Bioimaging of metallothioneins in ocular tissue sections by laser ablation-ICP-MS using bioconjugated gold nanoclusters as specific tags.

PubMed

Cruz-Alonso, María; Fernandez, Beatriz; Álvarez, Lydia; González-Iglesias, Héctor; Traub, Heike; Jakubowski, Norbert; Pereiro, Rosario

2017-12-18

An immunohistochemical method is described to visualize the distribution of metallothioneins 1/2 (MT 1/2) and metallothionein 3 (MT 3) in human ocular tissue. It is making use of (a) antibodies conjugated to gold nanoclusters (AuNCs) acting as labels, and (b) laser ablation (LA) coupled to inductively coupled plasma - mass spectrometry (ICP-MS). Water-soluble fluorescent AuNCs (with an average size of 2.7 nm) were synthesized and then conjugated to antibody by carbodiimide coupling. The surface of the modified AuNCs was then blocked with hydroxylamine to avoid nonspecific interactions with biological tissue. Immunoassays for MT 1/2 and MT 3 in ocular tissue sections (5 μm thick) from two post mortem human donors were performed. Imaging studies were then performed by fluorescence using confocal microscopy, and LA-ICP-MS was performed in the retina to measure the signal for gold. Signal amplification by the >500 gold atoms in each nanocluster allowed the antigens (MT 1/2 and MT 3) to be imaged by LA-ICP-MS using a laser spot size as small as 4 μm. The image patterns found in retina are in good agreement with those obtained by conventional fluorescence immunohistochemistry which was used as an established reference method. Graphical abstract Gold nanoclusters (AuNCs) conjugated to a primary specific antibody serve as a label for amplified bioimaging of metallothioneins (MTs) by laser ablation coupled to inductively coupled plasma - mass spectrometry (ICP-MS) in human ocular tissue sections.

Trace element analysis of synthetic mono- and poly-crystalline CaF 2 by ultraviolet laser ablation inductively coupled plasma mass spectrometry at 266 and 193 nm

NASA Astrophysics Data System (ADS)

Koch, J.; Feldmann, I.; Hattendorf, B.; Günther, D.; Engel, U.; Jakubowski, N.; Bolshov, M.; Niemax, K.; Hergenröder, R.

2002-06-01

The analytical figures of merit for ultraviolet laser ablation-inductively coupled plasma mass spectrometry (UV-LA-ICP-MS) at 266 nm with respect to the trace element analysis of high-purity, UV-transmitting alkaline earth halides are investigated and discussed. Ablation threshold energy density values and ablation rates for mono- and poly-crystalline CaF 2 samples were determined. Furthermore, Pb-, Rb-, Sr-, Ba- and Yb-specific analysis was performed. For these purposes, a pulsed Nd:YAG laser operated at the fourth harmonic of the fundamental wavelength (λ=266 nm) and a double-focusing sector field ICP-MS detector were employed. Depending on the background noise and isotope-specific sensitivity, the detection limits typically varied from 0.7 ng/g for Sr to 7 ng/g in the case of Pb. The concentrations were determined using a glass standard reference material (SRM NIST612). In order to demonstrate the sensitivity of the arrangement described, comparative measurements by means of a commercial ablation system consisting of an ArF excimer laser (λ=193 nm) and a quadrupole-type ICP-MS (ICP-QMS) instrument were carried out. The accuracy of both analyses was in good agreement, whereas ablation at 266 nm and detection using sector-field ICP-MS led to a sensitivity that was one order of magnitude above that obtained at 193 nm with ICP-QMS.

Laser ablation inductively coupled plasma mass spectrometry for direct isotope ratio measurements on solid samples

NASA Astrophysics Data System (ADS)

Pickhardt, Carola; Dietze, Hans-Joachim; Becker, J. Sabine

2005-04-01

Isotope ratio measurements have been increasingly used in quite different application fields, e.g., for the investigation of isotope variation in nature, in geoscience (geochemistry and geochronology), in cosmochemistry and planetary science, in environmental science, e.g., in environmental monitoring, or by the application of the isotope dilution technique for quantification purposes using stable or radioactive high-enriched isotope tracers. Due to its high sensitivity, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is today a challenging mass spectrometric technique for the direct determination of precise and accurate isotope ratios in solid samples. In comparison to laser ablation quadrupole ICP-MS (LA-ICP-QMS), laser ablation coupled to a double-focusing sector field ICP-MS (LA-ICP-SFMS) with single ion detection offers a significant improvement of sensitivity at low mass resolution, whereby isotope ratios can be measured with a precision to 0.1% relative standard deviation (R.S.D.). In LA-ICP-SFMS, many disturbing isobaric interferences of analyte and molecular ions can be separated at the required mass resolution (e.g., 40Ar16O+ and 56Fe+ for iron isotope ratio measurements). The precision on isotope ratio measurements was improved by one order of magnitude via the simultaneous detection of mass-separated ion currents of isotopes using multiple ion collectors in LA-ICP-MS (LA-MC-ICP-MS). The paper discusses the state of the art, the challenges and limits in isotope ratio measurements by LA-ICP-MS using different instrumentations at the trace and ultratrace level in different fields of application as in environmental and biological research, geochemistry and geochronology with respect to their precision and accuracy.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buerger, Stefan; Riciputi, Lee R; Bostick, Debra A

2006-01-01

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

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

NASA Astrophysics Data System (ADS)

Becker, J. Sabine

2005-04-01

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

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.

Tandem Laser Induced Breakdown Spectroscopy (LIBS), Laser Ablation Inductively Coupled Plasma Mass Spectroscopy (LA-ICP-MS) and/or Laser Ablation Inductively Coupled Plasma Optical Emission Spectroscopy (LA-ICP-OES) for the analysis of samples of geological interest

NASA Astrophysics Data System (ADS)

Oropeza, D.

2016-12-01

A highly innovative laser ablation sampling instrument (J200 Tandem LA - LIBS) that combines the capabilities and analytical benefits of LIBS, LA-ICP-MS and LA-ICP-OES was used for micrometer-scale, spatially-resolved, elemental analysis of a wide variety of samples of geological interest. Data collected using ablation systems consisted of nanosecond (Nd:YAG operated 266nm) and femtosecond lasers (1030 and 343nm). An ICCD LIBS detector and Quadrupole based mass spectrometer were selected for LIBS and ICP-MS detection, respectively. This tandem instrument allows simultaneous determination of major and minor elements (for example, Si, Ca, Na, and Al, and trace elements such as Li, Ce, Cr, Sr, Y, Zn, Zr among others). The research also focused on elemental mapping and calibration strategies, specifically the use of emission and mass spectra for multivariate data analysis. Partial Least Square Regression (PLSR) is shown to minimize and compensate for matrix effects in the emission and mass spectra improving quantitative analysis by LIBS and LA-ICP-MS, respectively. The study provides a benchmark to evaluate analytical results for more complex geological sample matrices.

Elemental bioimaging by means of LA-ICP-OES: investigation of the calcium, sodium and potassium distribution in tobacco plant stems and leaf petioles.

PubMed

Thyssen, G M; Holtkamp, M; Kaulfürst-Soboll, H; Wehe, C A; Sperling, M; von Schaewen, A; Karst, U

2017-06-21

Laser ablation-inductively coupled plasma-optical emission spectroscopy (LA-ICP-OES) is presented as a valuable tool for elemental bioimaging of alkali and earth alkali elements in plants. Whereas LA-ICP-OES is commonly used for micro analysis of solid samples, laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) has advanced to the gold standard for bioimaging. However, especially for easily excitable and ubiquitous elements such as alkali and earth alkali elements, LA-ICP-OES holds some advantages regarding simultaneous detection, costs, contamination, and user-friendliness. This is demonstrated by determining the calcium, sodium and potassium distribution in tobacco plant stem and leaf petiole tissues. A quantification of the calcium contents in a concentration range up to 1000 μg g -1 using matrix-matched standards is presented as well. The method is directly compared to a LA-ICP-MS approach by analyzing parallel slices of the same samples.

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.

Using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to characterize copper, zinc and mercury along grizzly bear hair providing estimate of diet.

PubMed

Noël, Marie; Christensen, Jennie R; Spence, Jody; Robbins, Charles T

2015-10-01

We enhanced an existing technique, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), to function as a non-lethal tool in the temporal characterization of trace element exposure in wild mammals. Mercury (Hg), copper (Cu), cadmium (Cd), lead (Pb), iron (Fe) and zinc (Zn) were analyzed along the hair of captive and wild grizzly bears (Ursus arctos horribilis). Laser parameters were optimized (consecutive 2000 μm line scans along the middle line of the hair at a speed of 50 μm/s; spot size=30 μm) for consistent ablation of the hair. A pressed pellet of reference material DOLT-2 and sulfur were used as external and internal standards, respectively. Our newly adapted method passed the quality control tests with strong correlations between trace element concentrations obtained using LA-ICP-MS and those obtained with regular solution-ICP-MS (r(2)=0.92, 0.98, 0.63, 0.57, 0.99 and 0.90 for Hg, Fe, Cu, Zn, Cd and Pb, respectively). Cross-correlation analyses revealed good reproducibility between trace element patterns obtained from hair collected from the same bear. One exception was Cd for which external contamination was observed resulting in poor reproducibility. In order to validate the method, we used LA-ICP-MS on the hair of five captive grizzly bears fed known and varying amounts of cutthroat trout over a period of 33 days. Trace element patterns along the hair revealed strong Hg, Cu and Zn signals coinciding with fish consumption. Accordingly, significant correlations between Hg, Cu, and Zn in the hair and Hg, Cu, and Zn intake were evident and we were able to develop accumulation models for each of these elements. While the use of LA-ICP-MS for the monitoring of trace elements in wildlife is in its infancy, this study highlights the robustness and applicability of this newly adapted method. Copyright © 2015 Elsevier B.V. All rights reserved.

Deposition and element fractionation processes during atmospheric pressure laser sampling for analysis by ICP-MS

NASA Astrophysics Data System (ADS)

Eggins, S. M.; Kinsley, L. P. J.; Shelley, J. M. G.

1998-05-01

We have used an ArF excimer laser coupled to a quadrupole inductively coupled plasma mass spectrometry (ICP-MS) for the measurement of a range of elements during excavation of a deepening ablation pit in a synthetic glass (NIST 612). Analyte behaviour shows progressive volatile element enrichment at shallow hole depths, with a change to refractory element enrichment as the ablation pit deepens further. Examination of ablation pit morphology and the surface condensate deposited around the ablation site reveals the importance of sequential condensation of refractory, then volatile phases from the cooling plasma plume after the end of the laser pulse. We interpret the observed element fractionation behaviour to reflect a change in ablation processes from photothermal dominated to plasma dominated mechanisms. The development of the surface deposit is greatly reduced by ablating in an ambient atmosphere of He instead of Ar and is accompanied by a two- to four-fold increase in ICP-MS sensitivity.

A comparison of laser ablation-inductively coupled plasma-mass spectrometry and high-resolution continuum source graphite furnace molecular absorption spectrometry for the direct determination of bromine in polymers

NASA Astrophysics Data System (ADS)

de Gois, Jefferson S.; Van Malderen, Stijn J. M.; Cadorim, Heloisa R.; Welz, Bernhard; Vanhaecke, Frank

2017-06-01

This work describes the development and comparison of two methods for the direct determination of Br in polymer samples via solid sampling, one using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and the other using high-resolution continuum source graphite furnace molecular absorption spectrometry with direct solid sample analysis (HR-CS SS-GF MAS). The methods were optimized and their accuracy was evaluated by comparing the results obtained for 6 polymeric certified reference materials (CRMs) with the corresponding certified values. For Br determination with LA-ICP-MS, the 79Br+ signal could be monitored interference-free. For Br determination via HR-CS SS-GF MAS, the CaBr molecule was monitored at 625.315 nm with integration of the central pixel ± 1. Bromine quantification by LA-ICP-MS was performed via external calibration against a single CRM while using the 12C+ signal as an internal standard. With HR-CS SS-GF MAS, Br quantification could be accomplished using external calibration against aqueous standard solutions. Except for one LA-ICP-MS result, the concentrations obtained with both techniques were in agreement with the certified values within the experimental uncertainty as evidenced using a t-test (95% confidence level). The limit of quantification was determined to be 100 μg g- 1 Br for LA-ICP-MS and 10 μg g- 1 Br for HR-CS SS-GF MAS.

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

USGS Publications Warehouse

Nadoll, P.; Koenig, A.E.

2011-01-01

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

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

PubMed

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

2007-10-01

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

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

PubMed

Jantzi, Sarah C; Almirall, José R

2014-01-01

Elemental analysis of soil is a useful application of both laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS) in geological, agricultural, environmental, archeological, planetary, and forensic sciences. In forensic science, the question to be answered is often whether soil specimens found on objects (e.g., shoes, tires, or tools) originated from the crime scene or other location of interest. Elemental analysis of the soil from the object and the locations of interest results in a characteristic elemental profile of each specimen, consisting of the amount of each element present. Because multiple elements are measured, multivariate statistics can be used to compare the elemental profiles in order to determine whether the specimen from the object is similar to one of the locations of interest. Previous work involved milling and pressing 0.5 g of soil into pellets before analysis using LA-ICP-MS and LIBS. However, forensic examiners prefer techniques that require smaller samples, are less time consuming, and are less destructive, allowing for future analysis by other techniques. An alternative sample introduction method was developed to meet these needs while still providing quantitative results suitable for multivariate comparisons. The tape-mounting method involved deposition of a thin layer of soil onto double-sided adhesive tape. A comparison of tape-mounting and pellet method performance is reported for both LA-ICP-MS and LIBS. Calibration standards and reference materials, prepared using the tape method, were analyzed by LA-ICP-MS and LIBS. As with the pellet method, linear calibration curves were achieved with the tape method, as well as good precision and low bias. Soil specimens from Miami-Dade County were prepared by both the pellet and tape methods and analyzed by LA-ICP-MS and LIBS. Principal components analysis and linear discriminant analysis were applied to the multivariate data. Results from both the tape method and the pellet method were nearly identical, with clear groupings and correct classification rates of >94%.

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 evaporative phenomena were not sufficient to explain the dependence of aerosol detection on particle diameter. Additional work is needed to correlate experimental data with theory for metal-oxides where thermodynamic property data are sparse relative to pure elements. Lastly, when matrix effects and the diffusion of ions inside the plasma were considered, mass loading was concluded to have had an effect on the dependence of detection efficiency on particle diameter.

Liquid chromatography coupled with inductively coupled plasma mass spectrometry in the pharmaceutical industry: selected examples.

PubMed

Marshall, Peter S; Leavens, Bill; Heudi, Olivier; Ramirez-Molina, Cesar

2004-11-12

Both LC and capillary LC (CapLC) have been successfully interfaced with inductively coupled plasma mass spectrometry (ICP-MS). Gradients of acetonitrile and aqueous based solvents have been employed to separate several compounds of pharmaceutical interest. This paper will describe four application areas in the pharmaceutical industry, and examples will be shown where CapLC, LC and gel electrophoresis via laser ablation have been coupled with ICP-MS. The four areas highlighted in this paper are: (1) the use of derivatisation reactions to "make the invisible visible". Methods involving derivatisations with copper and iron will be described that can be used for the analysis of amines and carboxylic acids by ICP-MS. (2) The profiling of metal ion content (in particular bromine) in biological samples such as human plasma, this study will focus on the metabolism of bromine-labelled peptides (e.g. substance P). (3) The analysis of materials derived from single, solid-phase beads used in combinatorial chemistry, and (4) also discussed will be our findings from investigations into the use of laser ablation ICP-MS on the determination of protein phosphorylation on electrophoresis gel blots.

Sulfate and sulfide sulfur isotopes (δ34S and δ33S) measured by solution and laser ablation MC-ICP-MS: An enhanced approach using external correction

USGS Publications Warehouse

Pribil, Michael; Ridley, William I.; Emsbo, Poul

2015-01-01

Isotope ratio measurements using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) commonly use standard-sample bracketing with a single isotope standard for mass bias correction for elements with narrow-range isotope systems measured by MC-ICP-MS, e.g. Cu, Fe, Zn, and Hg. However, sulfur (S) isotopic composition (δ34S) in nature can range from at least − 40 to + 40‰, potentially exceeding the ability of standard-sample bracketing using a single sulfur isotope standard to accurately correct for mass bias. Isotopic fractionation via solution and laser ablation introduction was determined during sulfate sulfur (Ssulfate) isotope measurements. An external isotope calibration curve was constructed using in-house and National Institute of Standards and Technology (NIST) Ssulfate isotope reference materials (RM) in an attempt to correct for the difference. The ability of external isotope correction for Ssulfate isotope measurements was evaluated by analyzing NIST and United States Geological Survey (USGS) Ssulfate isotope reference materials as unknowns. Differences in δ34Ssulfate between standard-sample bracketing and standard-sample bracketing with external isotope correction for sulfate samples ranged from 0.72‰ to 2.35‰ over a δ34S range of 1.40‰ to 21.17‰. No isotopic differences were observed when analyzing Ssulfide reference materials over a δ34Ssulfide range of − 32.1‰ to 17.3‰ and a δ33S range of − 16.5‰ to 8.9‰ via laser ablation (LA)-MC-ICP-MS. Here, we identify a possible plasma induced fractionation for Ssulfate and describe a new method using external isotope calibration corrections using solution and LA-MC-ICP-MS.

Analysis of Trace Siderophile Elements at High Spatial Resolution Using Laser Ablation ICP-MS

NASA Astrophysics Data System (ADS)

Campbell, A. J.; Humayun, M.

2006-05-01

Laser ablation inductively coupled plasma mass spectometry is an increasingly important method of performing spatially resolved trace element analyses. Over the last several years we have applied this technique to measure siderophile element distributions at the ppm level in a variety of natural and synthetic samples, especially metallic phases in meteorites and experimental run products intended for trace element partitioning studies. These samples frequently require trace element analyses to be made at a finer spatial resolution (25 microns or better) than is frequently attained using LA-ICP-MS. In this presentation we review analytical protocols that were developed to optimize the LA-ICP-MS measurements for high spatial resolution. Particular attention is paid to the trade-offs involving sensitivity, ablation pit depth and diameter, background levels, and number of elements measured. To maximize signal/background ratios and avoid difficulties associated with ablating to depths greater than the ablation pit diameter, measurement involved integration of rapidly varying, transient but well-behaved signals. The abundances of platinum group elements and other siderophile elements in ferrous metals were calibrated against well-characterized standards, including iron meteorites and NIST certified steels. The calibrations can be set against the known abundance of an independently determined element, but normalization to 100 percent can also be employed, and was more useful in many circumstances. Evaluation of uncertainties incorporated counting statistics as well as a measure of instrumental uncertainty, determined by replicate analyses of the standards. These methods have led to a number of insights into the formation and chemical processing of metal in the early solar system.

In Situ Determination of Trace Elements in Fish Otoliths by Laser Ablation Double Focusing Sector Field Inductively Coupled Plasma Mass Spectrometry Using a Solution Standard Addition Calibration Method

NASA Astrophysics Data System (ADS)

Chen, Z.; Jones, C. M.

2002-05-01

Microchemistry of fish otoliths (fish ear bones) is a very useful tool for monitoring aquatic environments and fish migration. However, determination of the elemental composition in fish otolith by ICP-MS has been limited to either analysis of dissolved sample solution or measurement of limited number of trace elements by laser ablation (LA)- ICP-MS due to low sensitivity, lack of available calibration standards, and complexity of polyatomic molecular interference. In this study, a method was developed for in situ determination of trace elements in fish otoliths by laser ablation double focusing sector field ultra high sensitivity Finnigan Element 2 ICP-MS using a solution standard addition calibration method. Due to the lack of matrix-match solid calibration standards, sixteen trace elements (Na, Mg, P, Cr, Mn, Fe, Ni, Cu, Rb, Sr, Y, Cd, La, Ba, Pb and U) were determined using a solution standard calibration with Ca as an internal standard. Flexibility, easy preparation and stable signals are the advantages of using solution calibration standards. In order to resolve polyatomic molecular interferences, medium resolution (M/delta M > 4000) was used for some elements (Na, Mg, P, Cr, Mn, Fe, Ni, and Cu). Both external calibration and standard addition quantification strategies are compared and discussed. Precision, accuracy, and limits of detection are presented.

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

NASA Astrophysics Data System (ADS)

Girard, G.; Rooney, T. O.

2013-12-01

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

Usefulness of laser ablation ICP-MS for analysis of metallic particles released to oral mucosa after insertion of dental implants.

PubMed

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

2018-03-01

Despite the fact that titanium is considered highly biocompatible, its presence in the oral cavity (an environment of frequently changing pH and temperature) may result in the release of titanium from intraosseous implants into the oral mucosa, causing a range of reactions from the human body. Fragments of oral mucosa collected from patients after dental implant insertion were analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The study revealed an elevated content of elements (Ti, Al, V) which are components of the metal implants and temporary cover screws. Dynamic ablation of the tissue surface was used in order to obtain maps of the content and distribution of analyzed elements. The material consisted of 30 oral mucosa tissue fragments collected 3-5 months after implantation and 10 samples collected before implantation (control group). The application of optical microscope allowed for indication and confirmation of the location of metal particles prior to LA-ICP-MS analysis. The so-obtained map permitted location of regions containing metal particles. LA-ICP-MS analysis revealed groups of samples with similar properties of metal particles, thus confirming that those metal particles were the main source of the elevated content of metals (Ti, Al, V) in the tissue after implantation. A calibration strategy based on matrix matched solid standards with powdered egg white proteins as matrix material was applied with 34 S as an internal standard. The accuracy of the analytical method was verified by ablating pellets of certified reference material ERM-BB422 Fish muscle. Copyright © 2017 Elsevier GmbH. All rights reserved.

Simultaneous in situ determination of both U-Th-Pb and Sm-Nd isotopes in monazite by laser ablation using a magnetic sector ICP-MS and a multicollector ICP-MS

NASA Astrophysics Data System (ADS)

Goudie, D. J.; Fisher, C. M.; Hanchar, J. M.; Davis, W. J.; Crowley, J. L.; Ayers, J. C.

2012-12-01

We present a method for the simultaneous in situ determination of U-Th-Pb and Sm-Nd isotopes in monazite, using a laser ablation (LA) system coupled to both a magnetic sector inductively coupled plasma mass spectrometer (HR) ICP-MS and a multicollector (MC) ICP-MS. The ablated material is split using a glass Y-connector and transported simultaneously to both mass spectrometers via helium carrier gas. The MC-ICP-MS is configured to provide relative Ce, Gd, and Eu contents, in addition to Sm and Nd. This approach obtains both age (U-Pb), tracer isotope (Sm-Nd), and REE element data (Ce, Gd, and Eu), in the same ablation volume, thus reducing sampling problems associated with fine-scale zoning and other internal structures. The accuracy and precision of the U-Pb data are demonstrated using six well characterized monazite reference materials from the Geological Survey of Canada (three of which are currently used as SHRIMP standards) and agree well with previously determined ID-TIMS ages. The accuracy of the Sm-Nd isotopic data was assessed by comparison to TIMS measurements on a well-characterized in-house monazite standard. The dual LA-ICP-MS method was applied to the Birch Creek Pluton (BCP) in the White Mountains, California in a case study to test the utility of U-Th-Pb dating coupled with Sm-Nd (and Ce, Gd, Eu) isotopic data for solving geologic problems. Previous work on the Cretaceous BCP [1] used Th-Pb ages coupled with O isotopic data to constrain hydrothermal fluid events, as recorded in monazite. The original study suggested that the high delta 18O monazite in Paleozoic country rocks adjacent to the BCP grew in response to fluid alternation associated with the intrusion of the BCP, based on overlapping age with the BCP. New monazite split-stream U-Pb and Sm-Nd data show that monazite from the BCP pluton and monazite from altered country rock have homogenous and overlapping initial Nd isotopic composition, further strengthening the proposal that monazite in altered country rock can be a tracer of fluid alternation events. The split-stream U-Pb ages agrees with new high precision ID-TIMS U-Pb ages from the same monazite grains. These results demonstrate how monazite age and Sm-Nd isotopic data, coupled with delta 18O, can identify hydrothermal monazite and constrain the timing and potential sources of fluid events. [1] Ayers et al., Geology 34 (2006) 653-656.

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

PubMed

Seltzer, Michaeld; Berry, Kristinh

2005-03-01

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

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

USGS Publications Warehouse

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

2005-01-01

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

ARO - Terrestrial Research Program, Methodologies and Protocols for Characterization of Geomaterials

DTIC Science & Technology

2015-05-14

of ice involves melting, digestion, and analysis using inductively coupled plasma – mass spectrometry (ICPMS). ICP-MS analysis established elemental...4] have distinct chemical compositions. Knowledge of the chemical composition of the mineral assemblage present in a rock is critical to...activation analysis (INAA), to inductively-coupled plasma analysis and mass spectrometry (ICP & ICP-MS), mass spectrometry (MS), and laser-ablation

Imaging of Selenium by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) in 2-D Electrophoresis Gels and Biological Tissues.

PubMed

Cruz, Elisa Castañeda Santa; Susanne Becker, J; Sabine Becker, J; Sussulini, Alessandra

2018-01-01

Selenium and selenoproteins are important components of living organisms that play a role in different biological processes. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is a powerful analytical technique that has been employed to obtain distribution maps of selenium in biological tissues in a direct manner, as well as in selenoproteins, previously separated by their molecular masses and isoelectric points using two-dimensional polyacrylamide gel electrophoresis (2-D PAGE). In this chapter, we present the protocols to perform LA-ICP-MS imaging experiments, allowing the distribution visualization and determination of selenium and/or selenoproteins in biological systems.

Studies of LA-ICP-MS on quartz glasses at different wavelengths of a Nd:YAG laser.

PubMed

Becker, J S; Tenzler, D

2001-07-01

The capability of LA-ICP-MS for determination of trace impurities in transparent quartz glasses was investigated. Due to low or completely lacking absorption of laser radiation, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) proves difficult on transparent solids, and in particular the quantification of measurement results is problematic in these circumstances. Quartz glass reference materials of various compositions were studied by using a Nd:YAG laser system with focused laser radiation of wavelengths of 1064 nm, 532 nm and 266 nm, and an ICP-QMS (Elan 6000, Perkin Elmer). The influence of ICP and laser ablation conditions in the analysis of quartz glasses of different compositions was investigated, with the laser power density in the region of interaction between laser radiation and solid surface determining the ablation process. The trace element concentration was determined via calibration curves recorded with the aid of quartz glass reference materials. Under optimized measuring conditions the correlation coefficients of the calibration curves are in the range of 0.9-1. The relative sensitivity factors of the trace elements determined in the quartz glass matrix are 0.1-10 for most of the trace elements studied by LA-ICP-MS. The detection limits of the trace elements in quartz glass are in the low ng/g to pg/g range.

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

NASA Astrophysics Data System (ADS)

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

2002-08-01

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

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

PubMed

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

2010-11-01

Current profiling of rough diamond source is performed using different physical and/or morphological techniques that require strong knowledge and experience in the field. More recently, chemical impurities have been used to discriminate diamond source and with the advance of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) empirical profiling of rough diamonds is possible to some extent. In this study, we present a LA-ICP-MS methodology that we developed for analyzing ultra-trace element impurities in rough diamond for origin determination ("profiling"). Diamonds from two sources were analyzed by LA-ICP-MS and were statistically classified by accepted methods. For the two diamond populations analyzed in this study, binomial logistic regression produced a better overall correct classification than linear discriminant analysis. The results suggest that an anticipated matrix match reference material would improve the robustness of our methodology for forensic applications. © 2010 American Academy of Forensic Sciences.

Aerosol detection efficiency in inductively coupled plasma mass spectrometry

DOE PAGES

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 applied, but evaporative phenomena were not sufficient to explain the dependence of aerosol detection on particle diameter. Additional work is needed to correlate experimental data with theory for metal-oxides where thermodynamic property data are sparse relative to pure elements. Finally, when matrix effects and the diffusion of ions inside the plasma were considered, mass loading was concluded to have had an effect on the dependence of detection efficiency on particle diameter.« less

LA-ICP-MS depth profile analysis of apatite: Protocol and implications for (U-Th)/He thermochronometry

NASA Astrophysics Data System (ADS)

Johnstone, Samuel; Hourigan, Jeremy; Gallagher, Christopher

2013-05-01

Heterogeneous concentrations of α-producing nuclides in apatite have been recognized through a variety of methods. The presence of zonation in apatite complicates both traditional α-ejection corrections and diffusive models, both of which operate under the assumption of homogeneous concentrations. In this work we develop a method for measuring radial concentration profiles of 238U and 232Th in apatite by laser ablation ICP-MS depth profiling. We then focus on one application of this method, removing bias introduced by applying inappropriate α-ejection corrections. Formal treatment of laser ablation ICP-MS depth profile calibration for apatite includes construction and calibration of matrix-matched standards and quantification of rates of elemental fractionation. From this we conclude that matrix-matched standards provide more robust monitors of fractionation rate and concentrations than doped silicate glass standards. We apply laser ablation ICP-MS depth profiling to apatites from three unknown populations and small, intact crystals of Durango fluorapatite. Accurate and reproducible Durango apatite dates suggest that prolonged exposure to laser drilling does not impact cooling ages. Intracrystalline concentrations vary by at least a factor of 2 in the majority of the samples analyzed, but concentration variation only exceeds 5x in 5 grains and 10x in 1 out of the 63 grains analyzed. Modeling of synthetic concentration profiles suggests that for concentration variations of 2x and 10x individual homogeneous versus zonation dependent α-ejection corrections could lead to age bias of >5% and >20%, respectively. However, models based on measured concentration profiles only generated biases exceeding 5% in 13 of the 63 cases modeled. Application of zonation dependent α-ejection corrections did not significantly reduce the age dispersion present in any of the populations studied. This suggests that factors beyond homogeneous α-ejection corrections are the dominant source of overdispersion in apatite (U-Th)/He cooling ages.

Rare earth elements profile in a cultivated and non-cultivated soil determined by laser ablation-inductively coupled plasma mass spectrometry.

PubMed

Neves, Vinicius M; Heidrich, Graciela M; Hanzel, Flavia B; Muller, Edson I; Dressler, Valderi L

2018-05-01

Rare earth elements (REEs) have several applications but the effects on environment are not well known. Therefore, the aim of this work is to establish a method for direct solid sample analysis by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) to evaluate the concentration and distribution of REEs in cultivated and non-cultivated soil. Samples were collected in two areas to 40 cm of depth. The LA-ICP-MS method is easy to be implemented and the sample treatment is very fast comprising only its drying, grounding and pressing as a pellet. The accuracy of the method was evaluated by using a certified reference material (BCR 667 - Estuarine Sediment, Institute for Reference Materials and Measurements (IRMM)) where good agreement with the certified values was obtained. Analyte recovery at two levels of concentration (2.5 and 15.0 μg g -1 ) was also performed and recoveries in the range of 85%-120% were achieved, values that are acceptable for LA-ICP-MS analysis. In general, the concentration of the REEs is higher in the cultivated soil and increased from the surface to deeper layers, which can be a consequence of fertilizer application. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2014-09-01

In order to quantify and compare the uptake of aluminum oxide nanoparticles of three different sizes into two human cell lines (skin keratinocytes (HaCaT) and lung epithelial cells (A549)), three analytical methods were applied: digestion followed by nebulization inductively coupled plasma mass spectrometry (neb-ICP-MS), direct laser ablation ICP-MS (LA-ICP-MS), and flow cytometry. Light and electron microscopy revealed an accumulation and agglomeration of all particle types within the cell cytoplasm, whereas no particles were detected in the cell nuclei. The internalized Al2O3 particles exerted no toxicity in the two cell lines after 24 h of exposure. The smallest particles with a primary particle size ( x BET) of 14 nm (Alu1) showed the lowest sedimentation velocity within the cell culture media, but were calculated to have settled completely after 20 h. Alu2 ( x BET = 111 nm) and Alu3 ( x BET = 750 nm) were calculated to reach the cell surface after 7 h and 3 min, respectively. The internal concentrations determined with the different methods lay in a comparable range of 2-8 µg Al2O3/cm2 cell layer, indicating the suitability of all methods to quantify the nanoparticle uptake. Nevertheless, particle size limitations of analytical methods using optical devices were demonstrated for LA-ICP-MS and flow cytometry. Furthermore, the consideration and comparison of particle properties as parameters for particle internalization revealed the particle size and the exposure concentration as determining factors for particle uptake.

Applications of inductively coupled plasma mass spectrometry and laser ablation inductively coupled plasma mass spectrometry in materials science

NASA Astrophysics Data System (ADS)

Becker, Johanna Sabine

2002-12-01

Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) have been applied as the most important inorganic mass spectrometric techniques having multielemental capability for the characterization of solid samples in materials science. ICP-MS is used for the sensitive determination of trace and ultratrace elements in digested solutions of solid samples or of process chemicals (ultrapure water, acids and organic solutions) for the semiconductor industry with detection limits down to sub-picogram per liter levels. Whereas ICP-MS on solid samples (e.g. high-purity ceramics) sometimes requires time-consuming sample preparation for its application in materials science, and the risk of contamination is a serious drawback, a fast, direct determination of trace elements in solid materials without any sample preparation by LA-ICP-MS is possible. The detection limits for the direct analysis of solid samples by LA-ICP-MS have been determined for many elements down to the nanogram per gram range. A deterioration of detection limits was observed for elements where interferences with polyatomic ions occur. The inherent interference problem can often be solved by applying a double-focusing sector field mass spectrometer at higher mass resolution or by collision-induced reactions of polyatomic ions with a collision gas using an ICP-MS fitted with collision cell. The main problem of LA-ICP-MS is quantification if no suitable standard reference materials with a similar matrix composition are available. The calibration problem in LA-ICP-MS can be solved using on-line solution-based calibration, and different procedures, such as external calibration and standard addition, have been discussed with respect to their application in materials science. The application of isotope dilution in solution-based calibration for trace metal determination in small amounts of noble metals has been developed as a new calibration strategy. This review discusses new analytical developments and possible applications of ICP-MS and LA-ICP-MS for the quantitative determination of trace elements and in surface analysis for materials science.

Direct determination of platinum group elements and their distributions in geological and environmental samples at the ng g(-1) level using LA-ICP-IDMS.

PubMed

Boulyga, Sergei F; Heumann, Klaus G

2005-10-01

Laser ablation inductively coupled plasma isotope dilution mass spectrometry (LA-ICP-IDMS) was applied to the direct and simultaneous determination of the platinum group elements (PGEs) Pt, Pd, Ru, and Ir in geological and environmental samples. A special laser ablation system with high ablation rates was used, along with sector field ICP-MS. Special attention was paid to deriving the distributions of PGEs in the pulverized samples. IDMS could not be applied to the (mono-isotopic) Rh, but the similar ablation behavior of Ru and Rh allowed Rh to be simultaneously determined via relative sensitivity coefficients. The laser ablation process produces hardly any oxide ions (which usually cause interference in PGE analysis with liquid sample injection), so the ICP-MS can be run in its low mass resolution but high-sensitivity mode. The detection limits obtained for the geological samples were 0.16 ng g(-1), 0.14 ng g(-1), 0.08 ng g(-1), 0.01 ng g(-1) and 0.06 ng g(-1) for Ru, Rh, Pd, Ir and Pt, respectively. LA-ICP-IDMS was applied to different geological reference materials (TDB-1, WGB-1, UMT-1, WMG-1, SARM-7) and the road dust reference material BCR-723, which are only certified for some of the PGEs. Comparisons with certified values as well as with indicative values from the literature demonstrated the validity of the LA-ICP-IDMS method. The PGE concentrations in subsamples of the road dust reference material correspond to a normal distribution, whereas the distributions in the geological reference materials TDB-1, WGB-1, UMT-1, WMG-1, and SARM-7 are more complex. For example, in the case of Ru, a logarithmic normal distribution best fits the analyzed concentrations in TDB-1 subsamples, whereas a pronounced nugget effect was found for Pt in most geological samples.

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.

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

PubMed

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

2016-03-01

The study of the distribution of the cytostatic drugs cisplatin, carboplatin, and oxaliplatin along the kidney may help to understand their different nephrotoxic behavior. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) allows the acquisition of trace element images in biological tissues. However, results obtained are affected by several variations concerning the sample matrix and instrumental drifts. In this work, an internal standardization method based on printing an Ir-spiked ink onto the surface of the sample has been developed to evaluate the different distributions and accumulation levels of the aforementioned drugs along the kidney of a rat model. A conventional ink-jet printer was used to print fresh sagittal kidney tissue slices of 4 μm. A reproducible and homogenous deposition of the ink along the tissue was observed. The ink was partially absorbed on top of the tissue. Thus, this approach provides a pseudo-internal standardization, due to the fact that the ablation sample and internal standard take place subsequently and not simultaneously. A satisfactory normalization of LA-ICP-MS bioimages and therefore a reliable comparison of the kidney treated with different Pt-based drugs were achieved even for tissues analyzed on different days. Due to the complete ablation of the sample, the transport of the ablated internal standard and tissue to the inductively coupled plasma-mass spectrometry (ICP-MS) is practically taking place at the same time. Pt accumulation in the kidney was observed in accordance to the dosages administered for each drug. Although the accumulation rate of cisplatin and oxaliplatin is high in both cases, their Pt distributions differ. The strong nephrotoxicity observed for cisplatin and the absence of such side effect in the case of oxaliplatin could explain these distribution differences. The homogeneous distribution of oxaliplatin in the cortical and medullar areas could be related with its higher affinity for cellular transporters such as MATE2-k.

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

PubMed

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

2008-07-01

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

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

PubMed

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

2013-05-01

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Witte, Travis

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 inmore » particulate samples.« less

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

PubMed

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

2004-12-01

This paper describes a study designed to determine the possibility of using a dried aerosol solution for calibration in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The relative sensitivities of tested materials mobilized by laser ablation and by aqueous nebulization were established, and the experimentally determined relative sensitivity factors (RSFs) were used in conjunction with aqueous calibration for the analysis of solid steel samples. To such a purpose a set of CRM carbon steel samples (SS-451/1 to SS-460/1) were sampled into an ICP-MS instrument by solution nebulization using a microconcentric nebulizer with membrane desolvating (D-MCN) and by laser ablation (LA). Both systems were applied with the same ICP-MS operating parameters and the analyte signals were compared. The RSF (desolvated aerosol response/ablated solid response) values were close to 1 for the analytes Cr, Ni, Co, V, and W, about 1.3 for Mo, and 1.7 for As, P, and Mn. Complementary tests were carried out using CRM SS-455/1 as a solid standard for one-point calibration, applying LAMTRACE software for data reduction and quantification. The analytical results are in good agreement with the certified values in all cases, showing that the applicability of dried aerosol solutions is a good alternative calibration system for laser ablation sampling.

Quantitative analysis of major and trace elements in NH4HF2-modified silicate rock powders by laser ablation - inductively coupled plasma mass spectrometry.

PubMed

Zhang, Wen; Hu, Zhaochu; Liu, Yongsheng; Yang, Wenwu; Chen, Haihong; Hu, Shenghong; Xiao, Hongyan

2017-08-29

In this paper, we described a NH 4 HF 2 digestion method as sample preparation for the rapid determination of major and trace elements in silicate rocks using laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS). Sample powders digested by NH 4 HF 2 at 230 °C for 3 h form ultrafine powders with a typical grain size d 80  < 8.5 μm, and various silicate rocks have a consistent grain morphology and size, allowing us to produce pressed powder pellets that have excellent cohesion and homogeneity suitable for laser ablation micro-analysis without the addition of binder. The influences of the digestion parameters were investigated and optimized, including the evaporation stage of removing residual NH 4 HF 2 , sample homogenization, selection of the digestion vessel and calibration strategy of quantitative analysis. The optimized NH 4 HF 2 digestion method was applied to dissolve six silicate rock reference materials (BCR-2, BHVO-2, AGV-2, RGM-2, GSP-2, GSR-1) covering a wide range of rock types. Ten major elements and thirty-five trace elements were simultaneously analyzed by LA-ICP-MS. The analytical results of the six reference materials generally agreed with the recommended values, with discrepancies of less than 10% for most elements. The analytical precision is within 5% for most major elements and within 10% for most trace elements. Compared with previous methods of LA-ICP-MS bulk analysis, our method enables the complete dissolution of refractory minerals, such as zircon, in intermediate-acidic intrusive rocks and limits contamination as well as the loss of volatile elements. Moreover, there are many advantages for the new technique, including reducing matrix effects between reference materials and samples, spiking the internal standard simply and feasibly and sample batch processing. The applicability filed of the new technique in this study was focused on the whole-rock analysis of igneous rock samples, which are from basic rocks to acid rocks (45% < SiO 2  < 73%). However, we thought that the NH 4 HF 2 digestion method can be used as a new alternative in LA-ICP-MS for a wider range of geological samples, and will significantly accelerate the application of LA-ICP-MS for the whole-rock analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

Imaging of metal bioaccumulation in hay-scented fern (Dennstaedtia punctilobula) rhizomes growing on contaminated soils by laser ablation ICP-MS.

PubMed

Koelmel, Jeremy; Amarasiriwardena, Dulasiri

2012-09-01

Understanding Pb removal from the translocation stream is vital to engineering Pb hyperaccumulation in above ground organs, which would enhance the economic feasibility of Pb phytoextraction technologies. We investigated Cu, Pb, Sb and Zn distributions in Hay-scented fern (Dennstaedtia punctilobula) rhizomes on shooting range soils by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), analyzing digested rhizomes, stems, and fronds using ICP-MS. Nutrients Cu and Zn concentrated in fronds while toxic elements Pb and Sb did not, showing potential Pb and Sb sequestration in the rhizome. Frond and rhizome concentration of Pb was 0.17 ± 0.10% and 0.32 ± 0.21% of dry biomass, respectively. The 208Pb/13C and 121Sb/13C determined by LA-ICP-MS increased from inner sclerotic cortex to the epidermis, while Pb concentrated in the starchy cortex only in contaminated sites. These results suggest that concentration dependent bioaccumulation in the rhizome outer cortex removes Pb from the vascular transport stream. Copyright © 2012 Elsevier Ltd. All rights reserved.

High resolution mass spectrometric brain proteomics by MALDI-FTICR-MS combined with determination of P, S, Cu, Zn and Fe by LA-ICP-MS

NASA Astrophysics Data System (ADS)

Becker, J. Susanne; Zoriy, Miroslav; Przybylski, Michael; Becker, J. Sabine

2007-03-01

The combination of atomic and molecular mass spectrometric methods was applied for characterization and identification of several human proteins from Alzheimer's diseased brain. A brain protein mixture was separated by two-dimensional (2D) gel electrophoresis and the protein spots were fast screened by microlocal analysis using LA-ICP-MS (laser ablation inductively coupled plasma mass spectrometry) in respect to phosphorus, sulfur, copper, zinc and iron content. Five selected protein spots in 2D gel containing these elements were investigated after tryptic digestion by matrix assisted laser desorption ionization Fourier transform ion cyclotron resonance mass spectrometry (MALDI-FTICR-MS). Than element concentrations (P, Cu, Zn and Fe) were determined in three identified human brain proteins by LA-ICP-MS in the 2D gel. Results of structure analysis of human brain proteins by MALDI-FTICR-MS were combined with those of the direct determination of phosphorus, copper, zinc and iron concentrations in protein spots with LA-ICP-MS. From the results of atomic and molecular mass spectrometric techniques the human brain proteins were characterized in respect to their structure, sequence, phosphorylation state and metal content as well.

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

PubMed

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

2004-08-01

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

High spatial resolution analysis of ferromanganese concretions by LA-ICP-MS†

PubMed Central

Axelsson, Mikael D; Rodushkin, Ilia; Baxter, Douglas C; Ingri, Johan; Öhlander, Björn

2002-01-01

A procedure was developed for the determination of element distributions in cross-sections of ferromanganese concretions using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The effects of carrier flow rates, rf forward power, ablation energy, ablation spot size, repetition rate and number of shots per point on analyte intensity were studied. It is shown that different carrier gas flow rates are required in order to obtain maximum sensitivities for different groups of elements, thus complicating the optimisation of ICP parameters. On the contrary, LA parameters have very similar effects on almost all elements studied, thus providing a common optimum parameter set for the entire mass range. However, for selected LA parameters, the use of compromise conditions was necessary in order to compensate for relatively slow data acquisition by ICP-MS and maintain high spatial resolution without sacrificing the multielemental capabilities of the technique. Possible variations in ablation efficiency were corrected for mathematically using the sum of Fe and Mn intensities. Quantification by external calibration against matrix-matched standards was successfully used for more than 50 elements. These standards, in the form of pressed pellets (no binder), were prepared in-house using ferromanganese concentrates from a deep-sea nodule reference material as well as from shallow-marine concretions varying in size and having different proportions of three major phases: aluminosilicates, Fe- and Mn-oxyhydroxides. Element concentrations in each standard were determined by means of conventional solution nebulisation ICP-MS following acid digestion. Examples of selected inter-element correlations in distribution patterns along the cross-section of a concretion are given.

Application of LA-MC-ICP-MS for analysis of Sr isotope ratios in speleothems

NASA Astrophysics Data System (ADS)

Weber, Michael; Scholz, Denis; Wassenburg, Jasper A.; Jochum, Klaus Peter; Breitenbach, Sebastian

2017-04-01

Speleothems are well established climate archives. In order to reconstruct past climate variability, several geochemical proxies, such as δ13C and δ18O as well as trace elements are available. Since several factors influence each individual proxy, robust interpretation is often hampered. This calls for multi-proxy approaches involving additional isotope systems that can help to delineate the role of different sources of water within the epikarst and changes in soil composition. Sr isotope ratios (87Sr/86Sr) have been shown to provide useful information about water residence time and water mixing in the host rock. Furthermore, Sr isotopes are not fractionated during calcite precipitation, implying that the 87Sr/86Sr ratio of the speleothem provides a direct record of the drip water. While most speleothem studies applying Sr isotopes used the TIMS methodology, LA-MC-ICP-MS has been utilized for several other archives, such as otoliths and teeth. This method provides the advantage of faster data acquisition, higher spatial resolution, larger sample throughput and the absence of chemical treatment prior to analysis. Here we present the first LA-MC-ICP-MS Sr isotope data for speleothems. The analytical uncertainty of our LA-MC-ICP-MS Sr data is in a similar range as for other carbonate materials. The results of different ablation techniques (i.e. line scan and spots) are reproducible within error, implying that the application of this technique on speleothems is possible. In addition, several comparative measurements of different carbonate reference materials (i.e. MACS-3, JCt-1, JCp-1), such as tests with standard bracketing and comparison of the 87Sr/86Sr ratios with nanosecond laser ablation system and a state-of-the-art femtosecond laser ablation system, show the robustness of the method. We applied the method to samples from Morocco (Grotte de Piste) and India (Mawmluh Cave). Our results show only very small changes in the 87Sr/86Sr ratios of both speleothems. However, one speleothem from Mawmluh Cave shows a slight increase of 87Sr/86Sr within the error, which is reproducible with line scans and spots.

Strontium isotope measurement of basaltic glasses by laser ablation multiple collector inductively coupled plasma mass spectrometry based on a linear relationship between analytical bias and Rb/Sr ratios.

PubMed

Zhang, Le; Ren, Zhong-Yuan; Wu, Ya-Dong; Li, Nan

2018-01-30

In situ strontium (Sr) isotope analysis of geological samples by laser ablation multiple collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) provides useful information about magma mixing, crustal contamination and crystal residence time. Without chemical separation, during Sr isotope analysis with laser ablation, many kinds of interference ions (such as Rb + and Kr + ) are on the Sr isotope spectrum. Most previous in situ Sr isotope studies only focused on Sr-enriched minerals (e.g. plagioclase, calcite). Here we established a simple method for in situ Sr isotope analysis of basaltic glass with Rb/Sr ratio less than 0.14 by LA-MC-ICP-MS. Seven Faraday cups, on a Neptune Plus MC-ICP-MS instrument, were used to receive the signals on m/z 82, 83, 84, 85, 86, 87 and 88 simultaneously for the Sr isotope analysis of basaltic glass. The isobaric interference of 87 Rb was corrected by the peak stripping method. The instrumental mass fractionation of 87 Sr/ 86 Sr was corrected to 86 Sr/ 88 Sr = 0.1194 with an exponential law. Finally, the residual analytical biases of 87 Sr/ 86 Sr were corrected with a relationship between the deviation of 87 Sr/ 86 Sr from the reference values and the measured 87 Rb/ 86 Sr. The validity of the protocol present here was demonstrated by measuring the Sr isotopes of four basaltic glasses, a plagioclase crystal and a piece of modern coral. The measured 87 Sr/ 86 Sr ratios of all these samples agree within 100 ppm with the reference values. In addition, the Sr isotopes of olivine-hosted melt inclusions from the Emeishan large igneous province (LIP) were measured to show the application of our method to real geological samples. A simple but accurate approach for in situ Sr isotope measurement by LA-MC-ICP-MS has been established, which should greatly facilitate the wider application of in situ Sr isotope geochemistry, especially to volcanic rock studies. Copyright © 2017 John Wiley & Sons, Ltd.

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

NASA Technical Reports Server (NTRS)

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

2005-01-01

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

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

PubMed

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

2013-11-27

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

Precise and accurate in situ Pb-Pb dating of apatite, monazite, and sphene by laser ablation multiple-collector ICP-MS

NASA Astrophysics Data System (ADS)

Willigers, B. J. A.; Baker, J. A.; Krogstad, E. J.; Peate, D. W.

2002-03-01

To evaluate in situ Pb dating by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS), we analysed apatite, sphene, and monazite from Paleoproterozoic metamorphic rocks from West Greenland. Pb isotope ratios were also determined in the National Institute of Standards and Technology (NIST) 610 glass standard and were corrected for mass fractionation by reference to the measured thallium isotope ratio. The NIST 610 glass was used to monitor Pb isotope mass fractionation in the low Tl/Pb accessory minerals. Replicate analyses of the glass (1 to 2 min) yielded ratios with an external reproducibility comparable to conventional analyses of standard reference material 981 by thermal ionisation mass spectrometry (TIMS). Mineral grains were generally analysed with a 100-μm laser beam, although some monazite crystals were analysed at smaller spot sizes (10 and 25 μm). The common Pb isotope ratios required for age calculations were either measured on coexisting plagioclase by LA-MC-ICP-MS or could be ignored, as individual crystals exhibit sufficient Pb isotopic heterogeneity to perform isochron calculations on replicate analyses of single crystals. Mean mineral ages with the 204Pb ion beam measured in the multiplier were as follows: apatite, 1715 ± 23 m.y.; sphene, 1789 ± 11 m.y.; and monazite, 1783 to 1888 m.y., with relative uncertainties on individual monazite ages of <0.2% but highly reproducible age determinations on single monazite crystals (≪1%). Isochron ages calculated from several mineral analyses without assumption of common Pb also yield precise age determinations. Apatite and monazite Pb ages determined by in situ Pb isotope analysis are identical to those determined by conventional TIMS analysis of bulk mineral separates, and the analytical uncertainties of these short laser analyses with no prior mechanical or chemical separation are comparable to those obtained by TIMS. Detailed examination of the sphene in situ age data does, however, show a small discrepancy between the LA-MC-ICP-MS and TIMS ages (˜1% younger). High-resolution mass scans of the sphene during ablation clearly showed several small and as yet unidentified isobaric interferences that overlap with the 207Pb peak at the resolution conditions for measurement of isotope ratios. These might account for the age discrepancy between the LA-MC-ICP-MS and TIMS sphene ages. LA-MC-ICP-MS is a rapid, accurate, and precise method for in situ determination of Pb isotope ratios that can be used for geochronological studies in a manner similar to an ion microprobe, albeit currently at a somewhat degraded spatial resolution. Further modifications to the LA-MC-ICP-MS system, such as improved sensitivity, ion transmission, and LA methodology, may lead to this type of instrument becoming the method of choice for many types of in situ Pb isotope dating.

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

NASA Astrophysics Data System (ADS)

Boulyga, Sergei F.; Heumann, Klaus G.

2005-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2007-12-01

A comparison of 20 MORB glasses from 14°-16° N along the Mid-Atlantic Ridge using both solution-based and in situ laser ablation-based ICP-MS trace element analyses on the same samples was conducted. Li, Be, Sc, Ti, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Ba, La, Ce, Pr, Nd, Sm, Eu, Tb, Gd, Dy, Ho, Er, Tm, Yb,Lu, Hf, Ta, Pb, Th, and U were analyzed using the Varian 810 quadrupole ICP-MS. The instrument features a 90 degree ion mirror and low noise double-off-axis quadrupole that allows high sensitivity and low backgrounds. Precision in term of relative standard deviation (RSD) of the measurements for both methods based on repeated analyses of USGS BIR-1G and BHVO-2G glass standards and Max Planck KL-2G glass standard is within 5 % for all trace elements with the exception of Pb, which averaged 12 %. Measured trace element abundances are within 2% of recommended standard values using both solution and laser ablation methods. Comparison between the analyte concentrations obtained by solution-based ICP-MS and in situ microanalysis by laser ablation reveals little systematic differences in abundances(<5% for all elements). The two-method correlation and strong repeatability of the results indicate that rapid in situ trace element analysis by laser ablation ICP-MS is likely to become a preferred method of trace element analysis for MORB glasses. Our geochemical results and previous studies of MORB glasses in the region of the MAR between 14°-16°N show that basalts are characterized isotopic and incompatible element enrichment.The nature of the enrichment has been the topic of significant discussion and speculation because a specific mantle plume is not well defined in the region. Likewise the magma supply is probably small in the region as the magmatic crust is interpreted to be very thin in most of the area studied. Integrated studies of major element, trace element, and isotopic variations among basalts, gabbroic rocks and igneous and residual ultramafic rocks in the region indicate that 1) the enriched basalts have positive Ta-Nb anomalies, enriched relative to U, Th, and La 2) basalts have relatively high SiO2 abundances compared to the global average, 3) basalts show a HIMU isotopic signature, and 4) bulk major element abundances and mineral chemistry in mantle rocks indicate that they are among the most depleted,although variably refertilized, residual mantle assemblages sampled to date along MORs.We suggest that much of the regional variation in major and trace element data, as well as isotopic data and the unusual regional geology (multiple core complexes) can be explained by melting of a sub-axial mantle that contains two end members, one highly depleted and the other enriched. These components appear to involve ancient recycled ocean crust and lithospheric mantle.

Solid matrix transformation and tracer addition using molten ammonium bifluoride salt as a sample preparation method for laser ablation inductively coupled plasma mass spectrometry.

PubMed

Grate, Jay W; Gonzalez, Jhanis J; O'Hara, Matthew J; Kellogg, Cynthia M; Morrison, Samuel S; Koppenaal, David W; Chan, George C-Y; Mao, Xianglei; Zorba, Vassilia; Russo, Richard E

2017-09-08

Solid sampling and analysis methods, such as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), are challenged by matrix effects and calibration difficulties. Matrix-matched standards for external calibration are seldom available and it is difficult to distribute spikes evenly into a solid matrix as internal standards. While isotopic ratios of the same element can be measured to high precision, matrix-dependent effects in the sampling and analysis process frustrate accurate quantification and elemental ratio determinations. Here we introduce a potentially general solid matrix transformation approach entailing chemical reactions in molten ammonium bifluoride (ABF) salt that enables the introduction of spikes as tracers or internal standards. Proof of principle experiments show that the decomposition of uranium ore in sealed PFA fluoropolymer vials at 230 °C yields, after cooling, new solids suitable for direct solid sampling by LA. When spikes are included in the molten salt reaction, subsequent LA-ICP-MS sampling at several spots indicate that the spikes are evenly distributed, and that U-235 tracer dramatically improves reproducibility in U-238 analysis. Precisions improved from 17% relative standard deviation for U-238 signals to 0.1% for the ratio of sample U-238 to spiked U-235, a factor of over two orders of magnitude. These results introduce the concept of solid matrix transformation (SMT) using ABF, and provide proof of principle for a new method of incorporating internal standards into a solid for LA-ICP-MS. This new approach, SMT-LA-ICP-MS, provides opportunities to improve calibration and quantification in solids based analysis. Looking forward, tracer addition to transformed solids opens up LA-based methods to analytical methodologies such as standard addition, isotope dilution, preparation of matrix-matched solid standards, external calibration, and monitoring instrument drift against external calibration standards.

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.

Quantitative bioimaging of trace elements in the human lens by LA-ICP-MS.

PubMed

Konz, Ioana; Fernández, Beatriz; Fernández, M Luisa; Pereiro, Rosario; González-Iglesias, Héctor; Coca-Prados, Miguel; Sanz-Medel, Alfredo

2014-04-01

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for the quantitative imaging of Fe, Cu and Zn in cryostat sections of human eye lenses and for depth profiling analysis in bovine lenses. To ensure a tight temperature control throughout the experiments, a new Peltier-cooled laser ablation cell was employed. For quantification purposes, matrix-matched laboratory standards were prepared from a pool of human lenses from eye donors and spiked with standard solutions containing different concentrations of natural abundance Fe, Cu and Zn. A normalisation strategy was also carried out to correct matrix effects, lack of tissue homogeneity and/or instrumental drifts using a thin gold film deposited on the sample surface. Quantitative images of cryo-sections of human eye lenses analysed by LA-ICP-MS revealed a homogeneous distribution of Fe, Cu and Zn in the nuclear region and a slight increase in Fe concentration in the outer cell layer (i.e. lens epithelium) at the anterior pole. These results were assessed also by isotope dilution mass spectrometry, and Fe, Cu and Zn concentrations determined by ID-ICP-MS in digested samples of lenses and lens capsules.

Examination of the Mass Transfer of Additive Elements in Barium Titanate Ceramics during Sintering Process by Laser Ablation ICP-MS.

PubMed

Sakate, Daisuke; Iwazaki, Yoshiki; Kon, Yoshiaki; Yokoyama, Takaomi; Ohata, Masaki

2018-01-01

The mass transfer of additive elements during the sintering of barium titanate (BaTiO 3 ) ceramic was examined by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) in the present study. An analytical sample consisting of two pellets of BaTiO 3 with different concentrations of additive elements of manganese (Mn) and holmium (Ho) as well as silicon (Si) as a sintering reagent was prepared and measured by LA-ICP-MS with small laser irradiated diameter of 10 μm to evaluate the distributions and concentrations of additive elements in order to examine their mass transfers. As results, enrichments of Mn and Si as an additive element and a sintering reagent, respectively, were observed on the adhesive surface between two BaTiO 3 pellets, even though Ho did not show a similar phenomenon. The mass transfers of additive elements of Mn and Ho were also examined, and Mn seemed to show a larger mass transfer than that of Ho during the sintering process for BaTiO 3 ceramics. The results obtained in this study shows the effectives of LA-ICP-MS for the future improvement of MLCCs.

Hybrid Imaging Labels: Providing the Link Between Mass Spectrometry-Based Molecular Pathology and Theranostics

PubMed Central

Buckle, Tessa; van der Wal, Steffen; van Malderen, Stijn J.M.; Müller, Larissa; Kuil, Joeri; van Unen, Vincent; Peters, Ruud J.B.; van Bemmel, Margaretha E.M.; McDonnell, Liam A.; Velders, Aldrik H.; Koning, Frits; Vanhaeke, Frank; van Leeuwen, Fijs W. B.

2017-01-01

Background: Development of theranostic concepts that include inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) imaging can be hindered by the lack of a direct comparison to more standardly used methods for in vitro and in vivo evaluation; e.g. fluorescence or nuclear medicine. In this study a bimodal (or rather, hybrid) tracer that contains both a fluorescent dye and a chelate was used to evaluate the existence of a direct link between mass spectrometry (MS) and in vitro and in vivo molecular imaging findings using fluorescence and radioisotopes. At the same time, the hybrid label was used to determine whether the use of a single isotope label would allow for MS-based diagnostics. Methods: A hybrid label that contained both a DTPA chelate (that was coordinated with either 165Ho or 111In) and a Cy5 fluorescent dye was coupled to the chemokine receptor 4 (CXCR4) targeting peptide Ac-TZ14011 (hybrid-Cy5-Ac-TZ4011). This receptor targeting tracer was used to 1) validate the efficacy of (165Ho-based) mass-cytometry in determining the receptor affinity via comparison with fluorescence-based flow cytometry (Cy5), 2) evaluate the microscopic binding pattern of the tracer in tumor cells using both fluorescence confocal imaging (Cy5) and LA-ICP-MS-imaging (165Ho), 3) compare in vivo biodistribution patterns obtained with ICP-MS (165Ho) and radiodetection (111In) after intravenous administration of hybrid-Cy5-Ac-TZ4011 in tumor-bearing mice. Finally, LA-ICP-MS-imaging (165Ho) was linked to fluorescence-based analysis of excised tissue samples (Cy5). Results: Analysis with both mass-cytometry and flow cytometry revealed a similar receptor affinity, respectively 352 ± 141 nM and 245 ± 65 nM (p = 0.08), but with a much lower detection sensitivity for the first modality. In vitro LA-ICP-MS imaging (165Ho) enabled clear discrimination between CXCR4 positive and negative cells, but fluorescence microscopy was required to determine the intracellular distribution. In vivo biodistribution patterns obtained with ICP-MS (165Ho) and radiodetection (111In) of the hybrid peptide were shown to be similar. Assessment of tracer distribution in excised tissues revealed the location of tracer uptake with both LA-ICP-MS-imaging and fluorescence imaging. Conclusion: Lanthanide-isotope chelation expands the scope of fluorescent/radioactive hybrid tracers to include MS-based analytical tools such as mass-cytometry, ICP-MS and LA-ICP-MS imaging in molecular pathology. In contradiction to common expectations, MS detection using a single chelate imaging agent was shown to be feasible, enabling a direct link between nuclear medicine-based imaging and theranostic methods. PMID:28255355

High resolution analysis of trace elements in corals by laser ablation ICP-MS

NASA Astrophysics Data System (ADS)

Sinclair, Daniel J.; Kinsley, Leslie P. J.; McCulloch, Malcolm T.

1998-06-01

A method has been developed using laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) for rapid high resolution analysis of B, Mg, Sr, Ba, and U in corals. Corals represent a challenge for a microbeam technique due to their compositional and structural heterogeneity, their nonsilicate matrix, and their unusual range of trace element compositions relative to available standards. The method employs an argon-fluoride excimer laser (λ = 193 nm), masked to produce a beam 600 μm wide by 20 μm across to average ablation sampling over a range of structural features. Coral sections are scanned at a constant rate beneath the laser to produce a continuous sampling of the coral surface. Sensitivity drift is controlled by careful preconditioning of the ICP-MS to carbonate material, and standardisation is carried out by bracketing each traverse down the coral sample by analyses of a CaSiO 3 glass synthesised from coral powder. The method demonstrates excellent reproducibility of both the shape and magnitude of coralline trace element profiles, with typical precisions of between 1.0 and 3.7% based on analysis of the synthetic standard. Accuracy varies between 3.8% for B and 31% for U. Discrepancies are attributed to heterogeneities in the synthetic standard, and matrix differences between the silicate standard and carbonate sample. The method is demonstrated by analysis of a coral collected from Australia's Great Barrier Reef near a weather station recording in-situ sea-surface-temperature (SST). The elements B, Mg, Sr, and U show seasonal compositional cycles, and tentative calibrations against SST have been derived. Using independent ICP-MS solution estimates of the coral composition to correct for standardisation uncertainties, the following calibrations have been derived: B/Ca (μmol/mol)= 1000 (±20)- 20.6 (±0.8)× SSTMg/Ca (mmol/mol)= 0.0 (±0.3)+ 0.16 (±0.01)× SSTSr/Ca (mmol/mol)= 10.8 (±0.1)- 0.070 (±0.004)× SSTU/Ca (μmol/mol)= 2.24 (±0.07)- 0.046 (±0.003)× SSTl These calibrations agree with literature within experimental errors, except for Mg which displays a 35% greater temperature dependence than reported previously. None of the elements in the coral appear to be sensitive to decreases in salinity associated with heavy rainfall in the summer of 1991/1992.

Quantitative bioimaging by LA-ICP-MS: a methodological study on the distribution of Pt and Ru in viscera originating from cisplatin- and KP1339-treated mice.

PubMed

Egger, Alexander E; Theiner, Sarah; Kornauth, Christoph; Heffeter, Petra; Berger, Walter; Keppler, Bernhard K; Hartinger, Christian G

2014-09-01

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to study the spatially-resolved distribution of ruthenium and platinum in viscera (liver, kidney, spleen, and muscle) originating from mice treated with the investigational ruthenium-based antitumor compound KP1339 or cisplatin, a potent, but nephrotoxic clinically-approved platinum-based anticancer drug. Method development was based on homogenized Ru- and Pt-containing samples (22.0 and 0.257 μg g(-1), respectively). Averaging yielded satisfactory precision and accuracy for both concentrations (3-15% and 93-120%, respectively), however when considering only single data points, the highly concentrated Ru sample maintained satisfactory precision and accuracy, while the low concentrated Pt sample yielded low recoveries and precision, which could not be improved by use of internal standards ((115)In, (185)Re or (13)C). Matrix-matched standards were used for quantification in LA-ICP-MS which yielded comparable metal distributions, i.e., enrichment in the cortex of the kidney in comparison with the medulla, a homogenous distribution in the liver and the muscle and areas of enrichment in the spleen. Elemental distributions were assigned to histological structures exceeding 100 μm in size. The accuracy of a quantitative LA-ICP-MS imaging experiment was validated by an independent method using microwave-assisted digestion (MW) followed by direct infusion ICP-MS analysis.

Determination of tin isotope ratios in cassiterite by femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Schulze, Marie; Ziegerick, Marco; Horn, Ingo; Weyer, Stefan; Vogt, Carla

2017-04-01

In comparison to isotope analysis of dissolved samples femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry (fs-LA-MC-ICP-MS) enables precise isotope ratio analyses consuming much less sample material and with a minimum effort in sample preparation. This is especially important for the investigation of valuable historical objects for which visual traces of sampling are unwanted. The present study provides a basis for tin isotope ratio measurements using LA-MC-ICP-MS technique. For this, in house isotope standards had to be defined. Investigations on interferences and matrix effects illustrate that beside Sb only high Te contents (with values above those to be expected in cassiterite) result in a significant shift of the measured tin isotope ratios. This effect can partly be corrected for using natural isotope abundances. However, a natural isotope fractionation of Te cannot be excluded. Tin beads reduced from cassiterite were analysed by laser ablation and after dissolution. It was shown that tin isotope ratios can be determined accurately by using fs-LA-MC-ICP-MS. Furthermore the homogeneity of tin isotope ratios in cassiterite was proven.

Analysis of metal-binding proteins separated by non-denaturating gel electrophoresis using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

PubMed

Becker, J Susanne; Mounicou, Sandra; Zoriy, Miroslav V; Becker, J Sabine; Lobinski, Ryszard

2008-09-15

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) have become established as very efficient and sensitive biopolymer and elemental mass spectrometric techniques for studying metal-binding proteins (metalloproteins) in life sciences. Protein complexes present in rat tissues (liver and kidney) were separated in their native state in the first dimension by blue native gel electrophoresis (BN-PAGE). Essential and toxic metals, such as zinc, copper, iron, nickel, chromium, cadmium and lead, were detected by scanning the gel bands using quadrupole LA-ICP-MS with and without collision cell as a microanalytical technique. Several proteins were identified by using MALDI-TOF-MS together with a database search. For example, on one protein band cut from the BN-PAGE gel and digested with the enzyme trypsin, two different proteins - protein FAM44B and cathepsin B precursor - were identified. By combining biomolecular and elemental mass spectrometry, it was possible to characterize and identify selected metal-binding rat liver and kidney tissue proteins.

Evaluation of elemental profiling methods, including laser-induced breakdown spectroscopy (LIBS), for the differentiation of Cannabis plant material grown in different nutrient solutions.

PubMed

El-Deftar, Moteaa M; Robertson, James; Foster, Simon; Lennard, Chris

2015-06-01

Laser-induced breakdown spectroscopy (LIBS) is an emerging atomic emission based solid sampling technique that has many potential forensic applications. In this study, the analytical performance of LIBS, as well as that of inductively coupled plasma mass spectrometry (ICP-MS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and X-ray microfluorescence (μXRF), was evaluated for the ability to conduct elemental analyses on Cannabis plant material, with a specific investigation of the possible links between hydroponic nutrients and elemental profiles from associated plant material. No such study has been previously published in the literature. Good correlation among the four techniques was observed when the concentrations or peak areas of the elements of interest were monitored. For Cannabis samples collected at the same growth time, the elemental profiles could be related to the use of particular commercial nutrients. In addition, the study demonstrated that ICP-MS, LA-ICP-MS and LIBS are suitable techniques for the comparison of Cannabis samples from different sources, with high discriminating powers being achieved. On the other hand, μXRF method was not suitable for the discrimination of Cannabis samples originating from different growth nutrients. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and its Application in Life Sciences

NASA Astrophysics Data System (ADS)

Xu, Gu-feng; Wang, Hong-mei

2001-08-01

Inductively-coupled plasma mass spectrometry (ICP-MS) has made much progress since its birth in the late 1990s. This paper will give a rather systematic overview on the use of this technique in new devices and technologies related to plasma source, sample-introducing device and detecting spectrometer etc. In this overview, an emphasis will be put on the evaluation of the ICP-MS technique in combination with a series of physical, chemical and biological techniques, such as laser ablation (LA), capillary electrophoresis (CE) and high performance liquid chromatograph (HPLC), along with their representative high accuracy and high sensitivity. Finally, comprehensive and fruitful applications of the ICP-MS and its combinative techniques in the detection of trace metallic elements and isotopes in complex biological and environmental samples will be revealed.

RN12 and RN30 Epidote anlayses

DOE Data Explorer

Andrew Fowler

2015-01-01

Results for laser ablation measurement of reare earth elments and electron microprobe analysis of major elments in hydrothermal epidote. Laser ablation measurements were completed using an Agilent 7700 quadrupole ICP-MS coupled with 193nm Photon Instruments Excimer laser.

Isotope dilution ICP-MS with laser-assisted sample introduction for direct determination of sulfur in petroleum products.

PubMed

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

2005-08-01

Inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with direct laser-assisted introduction of isotope-diluted samples into the plasma, using a laser ablation system with high ablation rates, was developed for accurate sulfur determinations in different petroleum products such as 'sulfur-free' premium gasoline, diesel fuel, and heating oil. Two certified gas oil reference materials were analyzed for method validation. Two different 34S-enriched spike compounds, namely, elementary sulfur dissolved in xylene and dibenzothiophene in hexane, were synthesized and tested for their usefulness in this isotope dilution technique. The isotope-diluted sample was adsorbed on a filter-paper-like material, which was fixed in a special holder for irradiation by the laser beam. Under these conditions no time-dependent spike/analyte fractionation was only observed for the dibenzothiophene spike during the laser ablation process, which means that the measured 34S/32S isotope ratio of the isotope-diluted sample remained constant-a necessary precondition for accurate results with the isotope dilution technique. A comparison of LA-ICP-IDMS results with the certified values of the gas oil reference materials and with results obtained from ICP-IDMS analyses with wet sample digestion demonstrated the accuracy of the new LA-ICP-IDMS method in the concentration range of 9.2 microg g(-1) ('sulfur-free' premium gasoline) to 10.4 mg g(-1) (gas oil reference material BCR 107). The detection limit for sulfur by LA-ICP-IDMS is 0.04 microg g(-1) and the analysis time is only about 10 min, which therefore also qualifies this method for accurate determinations of low sulfur contents in petroleum products on a routine level.

Trace element study in scallop shells by laser ablation ICP-MS: the example of Ba/Ca ratios

NASA Astrophysics Data System (ADS)

Lorrain, A.; Pécheyran, C.; Paulet, Y.-M.; Chauvaud, L.; Amouroux, D.; Krupp, E.; Donard, O.

2003-04-01

As scallop shells grow incrementally at a rate of one line per day, environmental changes could then be evidenced on a daily basis. As an example for trace element incorporation studies, barium is a geochemical tracer that can be directly related to oceanic primary productivity. Hence, monitoring Ba/Ca variations in a scallop shell should give information about phytoplanktonic events encountered day by day during its life. The very high spatial resolution (typically 40 - 200 µm) and the high elemental sensitivity required can only be achieved by the combination of laser ablation coupled to inductively coupled plasma mass spectrometry. This study demonstrates that Laser ablation coupled to ICP-MS determination is a relevant tool for high resolution distribution measurement of trace elements in calcite matrix. The ablation strategy related to single line rastering and calcium normalisation were found to be the best analytical conditions in terms of reproducibility and sensitivity. The knowledge of P. maximus growth rings periodicity (daily), combined with LA-ICP-MS micro analysis allows the acquisition of time dated profiles with high spatial and thus temporal resolution. This resolution makes P. maximus a potential tool for environmental reconstruction and especially for accurate calibration of proxies. However, the relations among Ba/Ca peaks and phytoplanktonic events differed according to the animals and some inter-annual discrepancies complexify the interpretation.

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

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

NASA Astrophysics Data System (ADS)

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

2015-11-01

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

High sensitivity in-situ analysis of light lithophile (Li, Be, B) and alkali (Rb, Cs) elements by laser ablation magnetic sector ICP-MS: application to back arc basin magmatism

NASA Astrophysics Data System (ADS)

Kent, A. J.; Ungerer, C. A.

2003-12-01

Light lithophile (B, Be, Li) and alkali elements (Rb, Cs) provide many constraints on the origin and evolution of primitive magmatic rocks. However these elements are often present at low abundances, requiring large sample volumes, and may be strongly effected by alteration or sample contamination. We have developed a technique for rapid, in-situ, analysis of B, Be, Li, Rb and Cs abundances in glasses, glass inclusions and minerals using laser ablation microsampling and analysis by magnetic sector ICP-MS. By coupling the high sensitivity, dynamic range and low backgrounds of the ICP-MS with the speed and minimal sample preparation requirements of laser ablation, we can analyze these elements with detection limits that rival many solution-based techniques in ~60 s and using << 200 ng of material. Analyses are conducted using a NewWave DUV 193 nm ArF Excimer laser system, with He carrier gas. Samples were ablated at energies of 10-12 mJ/cm2 with pulse rates between 2-5 hz, and by either translating a 50 μ m laser spot over the surface at a rate of 5 μ m/s or by maintaining a stationary 50-70 μ m spot. Ablated material was analyzed with a VG Axiom single collector ICP-MS using a high-sensitivity sampler cone. All peaks were checked at high mass resolving power for molecular interferences, and analyses were conducted at low resolving power to maximize transmission. Careful monitoring of backgrounds was required for low-abundance measurements. Calculated detection limits are 1-2 ppb (Cs, Be), 5-10 ppb (Li) and 15-20 ppb (B, Rb). Surface contamination was removed with a pre-analysis ablation pass, and the small size of the laser spot allowed us to avoid altered and devitrified areas. Analysis of standard glasses showed excellent agreement with accepted values and repeat analyses suggest external errors are typically < 5-10%. Glasses from the Lau Basin show strong enrichments in B, Rb and Cs that correlate with a slab-fluid signature. B, Be Rb and Cs contents are very low in MORB-like samples from the north of the basin but are enriched in evolved lavas from propagating ridge tips.

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

PubMed

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

2014-09-01

Administering immunoregulatory cells to patients as medicinal agents is a potentially revolutionary approach to the treatment of immunologically mediated diseases. Presently, there are no satisfactory, clinically applicable methods of tracking human cells in patients with adequate spatial resolution and target cell specificity over a sufficient period of time. Laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) represents a potential solution to the problem of detecting very rare cells in tissues. In this article, this exquisitely sensitive technique is applied to the tracking of gold-labeled human regulatory macrophages (Mregs) in immunodeficient mice. Optimal conditions for labeling Mregs with 50-nm gold particles were investigated by exposing Mregs in culture to variable concentrations of label: Mregs incubated with 3.5 × 10(9) particles/ml for 1 h incorporated an average of 3.39 × 10(8) Au atoms/cell without loss of cell viability. Analysis of single, gold-labeled Mregs by LA-ICP-MS registered an average of 1.9 × 10(5) counts/cell. Under these conditions, 100% labeling efficiency was achieved, and label was retained by Mregs for ≥36 h. Gold-labeled Mregs adhered to glass surfaces; after 24 h of culture, it was possible to colabel these cells with human-specific (154)Sm-tagged anti-HLA-DR or (174)Yb-tagged anti-CD45 mAbs. Following injection into immunodeficient mice, signals from gold-labeled human Mregs could be detected in mouse lung, liver, and spleen for at least 7 d by solution-based inductively coupled plasma mass spectrometry and LA-ICP-MS. These promising results indicate that LA-ICP-MS tissue imaging has great potential as an analytical technique in immunology. Copyright © 2014 by The American Association of Immunologists, Inc.

Application of laser ablation multicollector inductively coupled plasma mass spectrometry for the measurement of calcium and lead isotope ratios in packaging for discriminatory purposes.

PubMed

Santamaria-Fernandez, Rebeca; Wolff, Jean-Claude

2010-07-30

The potential of high-precision calcium and lead isotope ratio measurements using laser ablation coupled to multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) to aid distinction between four genuine and five counterfeit pharmaceutical packaging samples and further classification of counterfeit packaging samples has been evaluated. We highlight the lack of reference materials for LA-MC-ICP-MS isotope ratio measurements in solids. In this case the problem is minimised by using National Institute of Standards and Technology Standard Reference Material (NIST SRM) 915a calcium carbonate (as solid pellets) and NIST SRM610 glass disc for sample bracketing external standardisation. In addition, a new reference material, NIST SRM915b calcium carbonate, has been characterised in-house for Ca isotope ratios and is used as a reference sample. Significant differences have been found between genuine and counterfeit samples; the method allows detection of counterfeits and aids further classification of packaging samples. Typical expanded uncertainties for measured-corrected Ca isotope ratio values ((43)Ca/(44)Ca and (42)Ca/(44)Ca) were found to be below 0.06% (k = 2, 95% confidence) and below 0.2% for measured-corrected Pb isotope ratios ((207)Pb/(206)Pb and (208)Pb/(206)Pb). This is the first time that Ca isotope ratios have been measured in packaging materials using LA coupled to a multicollector (MC)-ICP-MS instrument. The use of LA-MC-ICP-MS for direct measurement of Ca and Pb isotopic variations in cardboard/ink in packaging has definitive potential to aid counterfeit detection and classification. Copyright 2010 John Wiley & Sons, Ltd.

Precise and accurate isotope ratio measurements by ICP-MS.

PubMed

Becker, J S; Dietze, H J

2000-09-01

The precise and accurate determination of isotope ratios by inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) is important for quite different application fields (e.g. for isotope ratio measurements of stable isotopes in nature, especially for the investigation of isotope variation in nature or age dating, for determining isotope ratios of radiogenic elements in the nuclear industry, quality assurance of fuel material, for reprocessing plants, nuclear material accounting and radioactive waste control, for tracer experiments using stable isotopes or long-lived radionuclides in biological or medical studies). Thermal ionization mass spectrometry (TIMS), which used to be the dominant analytical technique for precise isotope ratio measurements, is being increasingly replaced for isotope ratio measurements by ICP-MS due to its excellent sensitivity, precision and good accuracy. Instrumental progress in ICP-MS was achieved by the introduction of the collision cell interface in order to dissociate many disturbing argon-based molecular ions, thermalize the ions and neutralize the disturbing argon ions of plasma gas (Ar+). The application of the collision cell in ICP-QMS results in a higher ion transmission, improved sensitivity and better precision of isotope ratio measurements compared to quadrupole ICP-MS without the collision cell [e.g., for 235U/238U approximately 1 (10 microg x L(-1) uranium) 0.07% relative standard deviation (RSD) vs. 0.2% RSD in short-term measurements (n = 5)]. A significant instrumental improvement for ICP-MS is the multicollector device (MC-ICP-MS) in order to obtain a better precision of isotope ratio measurements (with a precision of up to 0.002%, RSD). CE- and HPLC-ICP-MS are used for the separation of isobaric interferences of long-lived radionuclides and stable isotopes by determination of spallation nuclide abundances in an irradiated tantalum target.

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

PubMed

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

2010-03-15

A study of LA-ICP-MS analysis of pressed powdered tungsten carbide precursors was performed to show the advantages and problems of nanosecond laser ablation of matrix-unified samples. Five samples with different compositions were pressed into pellets both with silver powder as a binder serving to keep the matrix unified, and without any binder. The laser ablation was performed by nanosecond Nd:YAG laser working at 213 nm. The particle formation during ablation of both sets of pellets was studied using an optical aerosol spectrometer allowing the measurement of particle concentration in two size ranges (10-250 nm and 0.25-17 microm) and particle size distribution in the range of 0.25-17 microm. Additionally, the structure of the laser-generated particles was studied after their collection on a filter using a scanning electron microscope (SEM) and the particle chemical composition was determined by an energy dispersive X-ray spectroscope (EDS). The matrix effect was proved to be reduced using the same silver powdered binder for pellet preparation in the case of the laser ablation of powdered materials. The LA-ICP-MS signal dependence on the element content present in the material showed an improved correlation for Co, Ti, Ta and Nb of the matrix-unified samples compared to the non-matrix-unified pellets. In the case of W, the ICP-MS signal of matrix-unified pellets was influenced by the changes in the particle formation. Copyright (c) 2009 Elsevier B.V. All rights reserved.

87Sr/86Sr isotope ratio analysis by laser ablation MC-ICP-MS in scales, spines, and fin rays as a nonlethal alternative to otoliths for reconstructing fish life history

USGS Publications Warehouse

Willmes, Malte; Glessner, Justin J. G.; Carleton, Scott A.; Gerrity, Paul C.; Hobbs, James A.

2016-01-01

Strontium isotope ratios (87Sr/86Sr) in otoliths are a well-established tool to determine origins and movement patterns of fish. However, otolith extraction requires sacrificing fish, and when working with protected or endangered species, the use of nonlethal samples such as scales, spines, and fin rays is preferred. Unlike otoliths that are predominantly aragonite, these tissues are composed of biological apatite. Laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) analysis of biological apatite can induce significant interference on mass 87, causing inaccurate 87Sr/86Sr measurements. To quantify this interference, we applied LA-MC-ICP-MS to three marine samples (white seabass (Atractoscion nobilis) otolith; green sturgeon (Acipenser medirostris) pectoral fin ray; salmon shark (Lamna ditropis) tooth), and freshwater walleye (Sander vitreus) otoliths, scales, and spines). Instrument conditions that maximize signal intensity resulted in elevated 87Sr/86Sr isotope ratios in the bioapatite samples, related to a polyatomic interference (40Ca31P16O, 40Ar31P16O). Retuning instrument conditions to reduce oxide levels removed this interference, resulting in accurate 87Sr/86Sr ratios across all tissue samples. This method provides a novel, nonlethal alternative to otolith analysis to reconstruct fish life histories.

Investigating the influence of standard staining procedures on the copper distribution and concentration in Wilson's disease liver samples 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

2017-12-01

The influence of rhodanine and haematoxylin and eosin (HE) staining on the copper distribution and concentration in liver needle biopsy samples originating from patients with Wilson's disease (WD), a rare autosomal recessive inherited disorder of the copper metabolism, is investigated. In contemporary diagnostic of WD, rhodanine staining is used for histopathology, since rhodanine and copper are forming a red to orange-red complex, which can be recognized in the liver tissue using a microscope. In this paper, a laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) method is applied for the analysis of eight different WD liver samples. Apart from a spatially resolved elemental detection as qualitative information, this LA-ICP-MS method offers also quantitative information by external calibration with matrix-matched gelatine standards. The sample set of this work included an unstained and a rhodanine stained section of each WD liver sample. While unstained sections of WD liver samples showed very distinct structures of the copper distribution with high copper concentrations, rhodanine stained sections revealed a blurred copper distribution with significant decreased concentrations in a range from 20 to more than 90%. This implies a copper removal from the liver tissue by complexation during the rhodanine staining. In contrast to this, a further HE stained sample of one WD liver sample did not show a significant decrease in the copper concentration and influence on the copper distribution in comparison to the unstained section. Therefore, HE staining can be combined with the analysis by means of LA-ICP-MS in two successive steps from one thin section of a biopsy specimen. This allows further information to be gained on the elemental distribution by LA-ICP-MS additional to results obtained by histological staining. Copyright © 2017 Elsevier GmbH. All rights reserved.

Metrological approach to quantitative analysis of clinical samples by LA-ICP-MS: A critical review of recent studies.

PubMed

Sajnóg, Adam; Hanć, Anetta; Barałkiewicz, Danuta

2018-05-15

Analysis of clinical specimens by imaging techniques allows to determine the content and distribution of trace elements on the surface of the examined sample. In order to obtain reliable results, the developed procedure should be based not only on the properly prepared sample and performed calibration. It is also necessary to carry out all phases of the procedure in accordance with the principles of chemical metrology whose main pillars are the use of validated analytical methods, establishing the traceability of the measurement results and the estimation of the uncertainty. This review paper discusses aspects related to sampling, preparation and analysis of clinical samples by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) with emphasis on metrological aspects, i.e. selected validation parameters of the analytical method, the traceability of the measurement result and the uncertainty of the result. This work promotes the introduction of metrology principles for chemical measurement with emphasis to the LA-ICP-MS which is the comparative method that requires studious approach to the development of the analytical procedure in order to acquire reliable quantitative results. Copyright © 2018 Elsevier B.V. All rights reserved.

Small Volume Isotopic Analysis of Zircon Using LA-MC-ICP-MS U-Pb and Lu-Hf and Sub-ng Amounts of Hf in Solution

NASA Astrophysics Data System (ADS)

Bauer, A.; Horstwood, M. S.

2016-12-01

Crust-mantle evolution studies are greatly informed by zircon U-Pb and Lu-Hf isotopic datasets and the ease with which these data can now be acquired has seen their application become commonplace. In order to deconvolute geochemical change and interpret geologic variation in complexly zoned zircons, this information is most ideally obtained on the smallest volume of zircon by successive SIMS U-Pb and LA-MC-ICP-MS Lu-Hf isotopic analyses. However, due to variations in zircon growth zone geometry at depth, the Lu-Hf analysis may not relate to the lower volume U-Pb analysis, potentially causing inaccuracy of the resultant age-corrected Hf isotope signature. Laser ablation split-stream methods are applied to be certain that U-Pb and Lu-Hf data represent the same volume of zircon, however, the sampling volume remains relatively large at 40x30µm1. Coupled ID-TIMS U-Pb and solution MC-ICP-MS Lu-Hf work traditionally utilize whole-zircon dissolution ( 10-50ng Hf), which has the potential to homogenize different zones of geologic significance within an analysis. Conversely, modern ID-TIMS U-Pb methods utilize microsampling of zircon grains, often providing < 5ng Hf, thereby challenging conventional Lu-Hf acquisition protocols to achieve the required precision. In order to obtain usable precision on minimal zircon volumes, we developed laser ablation methods using successive 25um spot U-Pb and Lu-Hf ablation pits with a combined depth of 18um, and low-volume solution introduction methods without Hf-REE separation utilizing Hf amounts as low as 0.4ng, while retaining an uncertainty level of ca. 1 ɛHf for both methods. We investigated methods of Yb interference correction and the potential for matrix effects, with a particular focus on the accurate quantification of 176Lu/177Hf. These improvements reduce the minimum amount of material required for U-Pb and Hf isotopic analysis of zircon by about an order of magnitude. 1Ibanez-Mejia et al (2015). PreRes, 267, 285-310.

Low pressure laser ablation coupled to inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Fliegel, Daniel; Günther, Detlef

2006-07-01

The particle size distribution in laser ablation inductively coupled plasma mass spectrometry is known to be a critical parameter for complete vaporization of particles. Any strategy to reduce the particle size distribution of laser generated aerosols has the potential to increase the ion signal intensity and to reduce fractionation effects. Due to the fact that vapor generation, nucleation, condensation, and agglomeration take place within an extremely short period of time, ablation under atmospheric pressure might not allow influencing these processes while under reduced pressure condition the cooling of the aerosol and therefore the condensation is expected to be slower. In this study, a low pressure laser ablation cell for the generation of laser aerosols was coupled to an ICP-MS. In contrast to the previously developed trapped ablation mode, the newly designed cell allows the adjustment of the pressure in the ablation cell between 20 and 1400 mbar prior to the ablation. Ablation experiments carried out using this configuration showed a dependence of the aerosol properties (size distribution and particle structure) on the ablation cell pressure. The intensity ratio U/Th measured as a figure of merit for complete vaporization within the ICP indicated a change in the aerosol structure at approximately 500 mbar toward smaller particle size. A significant difference between low pressure and at ambient pressure ablated aerosol was observed. The intensity ratios (U/Th) of the ablated sample moves closer to the bulk composition at lower pressures at the expense of sensitivity. Therefore the decrease in the ICP-MS signal intensity in the low pressure cell can be attributed to vapor deposition within the ablation cell walls. Moreover, scanning electron microscope images of aerosols collected on filters after the low pressure ablation cell suggest the possibility of a slower cooling velocity of the aerosol, which was observed in the condensed material on the surface of ejected spherical particles. The expansion of the laser aerosol was also investigated using polished brass substrates in the expansion path-way for particle collection.

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

NASA Astrophysics Data System (ADS)

Mason, P. R.

2004-05-01

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

Development of a multi-variate calibration approach for quantitative analysis of oxidation resistant Mo-Si-B coatings using laser ablation inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Cakara, Anja; Bonta, Maximilian; Riedl, Helmut; Mayrhofer, Paul H.; Limbeck, Andreas

2016-06-01

Nowadays, for the production of oxidation protection coatings in ultrahigh temperature environments, alloys of Mo-Si-B are employed. The properties of the material, mainly the oxidation resistance, are strongly influenced by the Si to B ratio; thus reliable analytical methods are needed to assure exact determination of the material composition for the respective applications. For analysis of such coatings, laser ablation inductively coupled mass spectrometry (LA-ICP-MS) has been reported as a versatile method with no specific requirements on the nature of the sample. However, matrix effects represent the main limitation of laser-based solid sampling techniques and usually the use of matrix-matched standards for quantitative analysis is required. In this work, LA-ICP-MS analysis of samples with known composition and varying Mo, Si and B content was carried out. Between known analyte concentrations and derived LA-ICP-MS signal intensities no linear correlation could be found. In order to allow quantitative analysis independent of matrix effects, a multiple linear regression model was developed. Besides the three target analytes also the signals of possible argides (40Ar36Ar and 98Mo40Ar) as well as detected impurities of the Mo-Si-B coatings (108Pd) were considered. Applicability of the model to unknown samples was confirmed using external validation. Relative deviations from the values determined using conventional liquid analysis after sample digestion between 5 and 10% for the main components Mo and Si were observed.

Zinc isotope ratio imaging of rat brain thin sections from stable isotope tracer studies by LA-MC-ICP-MS.

PubMed

Urgast, Dagmar S; Hill, Sarah; Kwun, In-Sook; Beattie, John H; Goenaga-Infante, Heidi; Feldmann, Jörg

2012-10-01

Zinc stable isotope tracers (⁶⁷Zn and ⁷⁰Zn) were injected into rats at two different time points to investigate the feasibility of using tracers to study zinc kinetics at the microscale within distinct tissue features. Laser ablation coupled to multi-collector ICP-MS was used to analyse average isotope ratios in liver thin sections and to generate bio-images showing zinc isotope ratio distribution in brain thin sections. Average isotope ratios of all samples from treated animals were found to be statistically different (P < 0.05) from samples from untreated control animals. Furthermore, differing isotope ratios in physiological features of the brain, namely hippocampus, amygdala, cortex and hypothalamus, were identified. This indicates that these regions differ in their zinc metabolism kinetics. While cortex and hypothalamus contain more tracer two days after injection than 14 days after injection, the opposite is true for hippocampus and amygdala. This study showed that stable isotope tracer experiments can be combined with laser ablation MC-ICP-MS to measure trace element kinetics in tissues at a microscale level.

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

PubMed

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

2006-06-15

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

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

PubMed

Giussani, Barbara; Monticelli, Damiano; Rampazzi, Laura

2009-03-02

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

Fusion Bead Procedure for Nuclear Forensics Employing Synthetic Enstatite to Dissolve Uraniferous and Other Challenging Materials Prior to Laser Ablation Inductively Coupled Plasma Mass Spectrometry.

PubMed

Reading, David G; Croudace, Ian W; Warwick, Phillip E

2017-06-06

There is an increasing demand for rapid and effective analytical tools to support nuclear forensic investigations of seized or suspect materials. Some methods are simply adapted from other scientific disciplines and can effectively be used to rapidly prepare complex materials for subsequent analysis. A novel sample fusion method is developed, tested, and validated to produce homogeneous, flux-free glass beads of geochemical reference materials (GRMs), uranium ores, and uranium ore concentrates (UOC) prior to the analysis of 14 rare earth elements (REE) via laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The novelty of the procedure is the production of glass beads using 9 parts high purity synthetic enstatite (MgSiO 3 ) as the glass former with 1 part of sample (sample mass ∼1.5 mg). The beads are rapidly prepared (∼10 min overall time) by fusing the blended mixture on an iridium strip resistance heater in an argon-purged chamber. Many elements can be measured in the glass bead, but the rare earth group in particular is a valuable series in nuclear forensic studies and is well-determined using LA-ICP-MS. The REE data obtained from the GRMs, presented as chondrite normalized patterns, are in very good agreement with consensus patterns. The UOCs have comparable patterns to solution ICP-MS methods and published data. The attractions of the current development are its conservation of sample, speed of preparation, and suitability for microbeam analysis, all of which are favorable for nuclear forensics practitioners and geochemists requiring REE patterns from scarce or valuable samples.

Trace and surface analysis of ceramic layers of solid oxide fuel cells by mass spectrometry.

PubMed

Becker, J S; Breuer, U; Westheide, J; Saprykin, A I; Holzbrecher, H; Nickel, H; Dietze, H J

1996-06-01

For the trace analysis of impurities in thick ceramic layers of a solid oxide fuel cell (SOFC) sensitive solid-state mass spectrometric methods, such as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and radiofrequency glow discharge mass spectrometry (rf-GDMS) have been developed and used. In order to quantify the analytical results of LA-ICP-MS, the relative sensitivity coefficients of elements in a La(0.6)Sr(0.35)MnO(3) matrix have been determined using synthetic standards. Secondary ion mass spectrometry (SIMS) - as a surface analytical method - has been used to characterize the element distribution and diffusion profiles of matrix elements on the interface of a perovskite/Y-stabilized ZrO(2) layer. The application of different mass spectrometric methods for process control in the preparation of ceramic layers for the SOFC is described.

Laser ablation ICP-MS analysis on nano-powder pellets and applications to granite bulk rock analysis

NASA Astrophysics Data System (ADS)

Wu, Shitou; Karius, Volker; Wörner, Gerhard

2017-04-01

Granites are a ubiquitous component of the continental crust and knowing their precise trace element signatures is essential in understanding the origins and evolution of the continental crust. ICP-MS bulk analysis of granite is generally conducted on solution after acid-digestion. However this technique has several deficiencies related to the difficulty of completely dissolving accessary minerals such as zircon and the instability/adsorption of high valence trace elements (Nb, Ta et al.) in acid solutions. The development of a nano-powder pellet technique by using wet milling procedure, and its combination with laser ablation ICP-MS has been proposed to overcome these problems. In this study, we produced nano-powders from a series of granite rock standards by wet milling in agate using a high power planetary ball mill instrument. The procedure was tested and optimized by modifying parameters (ball to powder ratio, water to powder ratio, milling power etc.). Characterization of nano-powders was conducted by various techniques including electron microprobe (EMP), secondary electron imaging, polarizing microscope, and laser particle size analyzer (LPSA) and laser scanning confocal microscope (LSCM). Particle sizes range from a few nm to 5 μm with a small secondary mode at around 10 to 20 μm that probably represent particle aggregates rather than remaining crystal grains after milling. Pellets of 5 mm in diameter were pressed into molds of cellulose at 1.75 *103 N/cm2. Surface roughness of the pellets was measured by LSCM and gave a Ra of 0.494 μm, which is an order higher than the surface of polished ATGH-G reference glass surface (Ra: 0.048 μm), but sufficient for laser ablation. Sources of contamination either from abrading agate balls or from ultrapure water were evaluated and quantified. The homogeneity of powder pellets down to less than 5 μm size was documented based on EMPA element mapping and statistical analyses of LA-ICP-MS in discrete spot and line scanning analytical mode. We report data from major to trace element (to < 0.1 ppm) of currently available international granite reference materials (JG-2, JG-3, GWB07103, GEB07111, GSP-2 and G-3) to evaluate analytical precision and accuracy of LA-ICP-MS measurements. Our results illustrate the potential of this method for high precision analysis of trace elements and e.g. Zr/Hf and Nb/Ta ratios in granites.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Havrilla, George Joseph; McIntosh, Kathryn Gallagher; Judge, Elizabeth

2016-10-20

Feasibility tests were conducted using femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry for rapid uranium isotopic measurements. The samples used in this study consisted of a range of pg quantities of known 235/238 U solutions as dried spot residues of 300 pL drops on silicon substrates. The samples spanned the following enrichments of 235U: 0.5, 1.5, 2, 3, and 15.1%. In this direct comparison using these particular samples both pulse durations demonstrated near equivalent data can be produced on either system with respect to accuracy and precision. There is no question that either LA-ICP-MS method offers themore » potential for rapid, accurate and precise isotopic measurements of U10Mo materials whether DU, LEU or HEU. The LA-ICP-MS equipment used for this work is commercially available. The program is in the process of validating this work for large samples using center samples strips from Y-12 MP-1 LEU-Mo Casting #1.« less

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.

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

NASA Technical Reports Server (NTRS)

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

2014-01-01

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

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

PubMed

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

2010-02-01

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

Rapid age determination of oysters using LA-ICP-MS line scans of shell Mg/Ca ratios

NASA Astrophysics Data System (ADS)

Gillikin, D. P.; Durham, S. R.; Goodwin, D. H.

2016-02-01

Magnesium to calcium (Mg/Ca) ratios exhibit a strong temperature dependence in foraminifera and corals, but not in bivalve mollusks. Various studies have reported Mg/Ca-temperature relationships with R2 values ranging from 0.3 to 0.8 and significantly different relationships for bivalves growing at different salinities. However, this poor temperature correlation does not render Mg/Ca data useless. A weak temperature dependence would allow time (seasons and years) to be determined along the growth axis of shells. This would provide information about age, growth rate and also allow other proxies to be aligned with time. Typically, oxygen isotopes (δ18O) are used to age shells without clear periodic growth lines, which is time consuming and expensive. Line scans using laser ablation systems can cover several centimeters of shell in a few minutes. We test this method on the resilifer of two oyster species (Crassostrea gigas and C. virginica) using a 193 nm Laser-Ablation-ICP-MS. Living oysters were collected from San Francisco Bay, North Carolina, South Carolina, and the Gulf of Mexico; fossil shells (Pleistocene) were also collected in South Carolina. Shells were sampled for δ18O values and Mg/Ca ratios. We use annual cycles in δ18O values to confidently determine age, then apply the Mg/Ca technique. Shells of both species exhibit annual cyclicity in Mg/Ca ratios using spot and line scan laser sampling, which matche the seasonal cyclicity determined using δ18O values. Results show a good correlation between ages determined using the different methods. We conclude that LA-ICP-MS line scans offer a rapid and inexpensive technique for determining age, growth rate, and timing of shell growth in oyster reslifers.

In Situ Carbon Isotope Analysis by Laser Ablation MC-ICP-MS.

PubMed

Chen, Wei; Lu, Jue; Jiang, Shao-Yong; Zhao, Kui-Dong; Duan, Deng-Fei

2017-12-19

Carbon isotopes have been widely used in tracing a wide variety of geological and environmental processes. The carbon isotope composition of bulk rocks and minerals was conventionally analyzed by isotope ratio mass spectrometry (IRMS), and, more recently, secondary ionization mass spectrometry (SIMS) has been widely used to determine carbon isotope composition of carbon-bearing solid materials with good spatial resolution. Here, we present a new method that couples a RESOlution S155 193 nm laser ablation system with a Nu Plasma II MC-ICP-MS, with the aim of measuring carbon isotopes in situ in carbonate minerals (i.e., calcite and aragonite). Under routine operating conditions for δ 13 C analysis, instrumental bias generally drifts by 0.8‰-2.0‰ in a typical analytical session of 2-3 h. Using a magmatic calcite as the standard, the carbon isotopic composition was determined for a suite of calcite samples with δ 13 C values in the range of -6.94‰ to 1.48‰. The obtained δ 13 C data are comparable to IRMS values. The combined standard uncertainty for magmatic calcite is <0.3‰ (1s). No significant matrix effects have been identified in calcite with the amplitude of chemical composition variation (i.e., MnO, SrO, MgO, or FeO) up to 2.5 wt %. Two modern corals were investigated using magmatic calcite as the calibration standard, and the average δ 13 C values for both corals are similar to the bulk IRMS values. Moreover, coral exhibits significant heterogeneity in carbon isotope compositions, with differences up to 4.85‰ within an individual coral. This study indicates that LA-MC-ICP-MS can serve as an appropriate method to analyze carbon isotopes of carbonate minerals in situ.

Iron isotope composition of particles produced by UV-femtosecond laser ablation of natural oxides, sulfides, and carbonates.

PubMed

d'Abzac, Francois-Xavier; Beard, Brian L; Czaja, Andrew D; Konishi, Hiromi; Schauer, James J; Johnson, Clark M

2013-12-17

The need for femtosecond laser ablation (fs-LA) systems coupled to MC-ICP-MS to accurately perform in situ stable isotope analyses remains an open question, because of the lack of knowledge concerning ablation-related isotopic fractionation in this regime. We report the first iron isotope analysis of size-resolved, laser-induced particles of natural magnetite, siderite, pyrrhotite, and pyrite, collected through cascade impaction, followed by analysis by solution nebulization MC-ICP-MS, as well as imaging using electron microscopy. Iron mass distributions are independent of mineralogy, and particle morphology includes both spheres and agglomerates for all ablated phases. X-ray spectroscopy shows elemental fractionation in siderite (C-rich agglomerates) and pyrrhotite/pyrite (S-rich spheres). We find an increase in (56)Fe/(54)Fe ratios of +2‰, +1.2‰, and +0.8‰ with increasing particle size for magnetite, siderite, and pyrrhotite, respectively. Fe isotope differences in size-sorted aerosols from pyrite ablation are not analytically resolvable. Experimental data are discussed using models of particles generation by Hergenröder and elemental/isotopic fractionation by Richter. We interpret the isotopic fractionation to be related to the iron condensation time scale, dependent on its saturation in the gas phase, as a function of mineral composition. Despite the isotopic variations across aerosol size fractions, total aerosol composition, as calculated from mass balance, confirms that fs-LA produces a stoichiometric sampling in terms of isotopic composition. Specifically, both elemental and isotopic fractionation are produced by particle generation processes and not by femtosecond laser-matter interactions. These results provide critical insights into the analytical requirements for laser-ablation-based stable isotope measurements of high-precision and accuracy in geological samples, including the importance of quantitative aerosol transport to the ICP.

Inductively coupled plasma mass spectrometry with a twin quadrupole instrument using laser ablation sample introduction and monodisperse dried microparticulate injection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Allen, Lloyd A.

1996-10-17

The focus of this dissertation is the use of a twin quadrupole inductively coupled plasma mass spectrometer (ICP-MS) for the simultaneous detection of two m/z values. The twin quadrupole ICP-MS is used with laser ablation sample introduction in both the steady state (10 Hz) and single pulse modes. Steady state signals are highly correlated and the majority of flicker noise cancels when the ratio is calculated. Using a copper sample, the isotope ratio 63Cu +/ 65Cu + is measured with a relative standard deviation (RSD) of 0.26%. Transient signals for single laser pulses are also obtained. Copper isotope ratio measurementsmore » for several laser pulses are measured with an RSD of 0.85%. Laser ablation (LA) is used with steel samples to assess the ability of the twin quadrupole ICP-MS to eliminate flicker noise of minor components of steel samples. Isotopic and internal standard ratios are measured in the first part of this work. The isotope ratio 52Cr +/ 53Cr + (Cr present at 1.31 %) can be measured with an RSD of 0.06 % to 0.1 %. For internal standard elements, RSDs improve from 1.9 % in the Cr + signal to 0.12% for the ratio of 51V + to 52Cr +. In the second part of this work, one mass spectrometer is scanned while the second channel measures an individual m/z value. When the ratio of these two signals is calculated, the peak shapes in the mass spectrum are improved significantly. Pulses of analyte and matrix ions from individual drops are measured simultaneously using the twin quadrupole ICP-MS with monodisperse dried microparticulate injection (MDMI). At modest Pb concentrations (500 ppm), a shoulder on the leading edge of the Li + signal becomes apparent. Space charge effects are consistent with the disturbances seen.« less

Single-Shot Laser Ablation Split-Stream (SS-LASS) Analysis Depth Profiling

NASA Astrophysics Data System (ADS)

Kylander-Clark, A. R.; Stearns, M. A.; Viete, D. R.; Cottle, J. M.; Hacker, B. R.

2014-12-01

Laser ablation depth profiling of geochronometers—such as zircon, monazite, titanite and rutile—has become popular in recent years as a tool to both determine date vs. depth or trace-element (TE) composition vs. depth; the former allows the dating of thin rims and, potentially, inversion of Pb-loss profiles for thermal histories, whereas the latter can yield insight into changes in PTX or mineral parageneses and inversion of trace-element profiles for thermal histories. In this study, we combine both techniques, enabling simultaneous acquisition of U-Th/Pb isotopic ratios and trace-element compositions, by joining a 193 nm excimer laser to a multi-collector ICP-MS and single-collector ICP-MS. The simultaneous acquisition allows direct shot-by-shot linkage between time and petrology, expanding our ability to understand the evolution of complex geologic systems. We construct each depth profile by capturing the analyte with a succession of individual laser pulses (each ~100 nm deep) . This has two main advantages over a typical time-dependent analysis of a multi-shot routine composed of tens to hundreds of shots and a several μm deep hole. 1) The reference material is analyzed between each shot for a more-accurate standardization of each aliquot of ablated material. 2) There is no mixing of material ablated from successive laser pulses during transmission to the ICP. The method is limited by count rate, which depends on spot size, excavation rate, instrument sensitivity, etc., and, for single-collector ICP, the switching time, which limits the number of elements that can be analyzed and their total counts. We explore the latter theoretically and experimentally to provide insight on both the ideal number of elements to measure and the dwell time in any given sample. Examples of the utility of SS-LASS include the comparison of apparent Pb loss to diffusion profiles of trace elements in rims of metamorphic rutile and titanite, as well as the determination of the timing and petrologic conditions of thin zircon rims in metamorphic rocks.

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

PubMed

Scarciglia, Fabio; Barca, Donatella

2017-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

Laurentide Ice Sheet Meltwater Geochemistry During the MIS 3 Warm Phase from Single-Shell Trace Element and Isotope Measurements

NASA Astrophysics Data System (ADS)

Branson, O.; Vetter, L.; Fehrenbacher, J. S.; Spero, H. J.

2016-12-01

The geochemical variability between individual foraminifera within single core intervals records both palaeo-oecanographic conditions and ecology. Within the biological context of foraminiferal species, this population variability may be interpreted to provide unparalleled paleoenvironmental information. For example, coupled trace element and stable isotope analyses of single O. universa offer a powerful tool for reconstructing the δ18O of Laurentide Ice Sheet (LIS) meltwater, by calculating the intercept between temperature-corrected δ18O water and Ba/Ca salinity estimates (Vetter et al., in review). This offers valuable insights into the dynamics of ice sheet melting at the end of the last glacial maximum. Here we apply similar coupled single-shell laser ablation (LA-ICP-MS) and isotope ratio mass spectrometry (IRMS) techniques to explore the δ18O of Laurentide meltwater during H4 and bracketing intervals. The application of these methods to down-core samples requires the development of robust LA-ICP-MS data processing techniques to identify primary signals within Ba contaminated samples, and careful consideration of palaeo Ba/Ca-salinity relationships. Our analyses offer a significant advance in systematic LA-ICP-MS data processing methods, offer constraints on the variability of riverine Ba fluxes, and ultimately provide δ18O estimates of LIS meltwater during H4.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sheng, Peng; Hu, Qinhong; Ewing, Robert P.

2012-03-01

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

Quantitative 3-D elemental mapping by LA-ICP-MS of a basaltic clast from the Hanford 300 Area, Washington, USA.

PubMed

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

2012-02-21

Laser ablation with inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to measure elemental concentrations at the 100-μm scale in a 3-dimensional manner within a basaltic clast sample collected from the Hanford 300 Area in south-central Washington State, United States. A calibration method was developed to quantify the LA-ICP-MS signal response using a constant-sum mass fraction of eight major elements; the method produced reasonable concentration measurements for both major and trace elements when compared to a standard basalt sample with known concentrations. 3-Dimensional maps (stacked 2-D contour layers, each representing 2100 μm × 2100 μm) show relatively uniform concentration with depth for intrinsic elements such as Si, Na, and Sr. However, U and Cu accumulation were observed near the sample surface, consistent with the site's release history of these contaminants. U and Cu show substantial heterogeneity in their concentration distributions within horizontal slices, while the intrinsic elements are essentially uniformly distributed. From these measured U concentrations and published grain size distributions, gravel and cobbles were estimated to contain about 1% of the contaminant U, implicating the coarse fraction as a long-term release source.

Laser Induced Breakdown Spectroscopy (LIBS)

DTIC Science & Technology

2010-03-31

mass spectrometry and laser induced breakdown spectroscopy, Spe T Trejos, A Flores and JR. Almirall, Micro-spectrochemical analysis of document paper...and gel inks by laser ablation inductively coupled plasma mass spectrometry and laser induced breakdown spectroscopy, Spectrochimica Acta Part B...abstracts): 1. *Schenk, E.R. “Elemental analysis of unprocessed cotton by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser

Elemental and Isotopic Analysis of Uranium Oxide an NIST Glass Standards by FEMTOSECOND-LA-ICP-MIC-MS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ebert, Chris; Zamzow, Daniel S.; McBay, Eddie H.

2009-06-01

The objective of this work was to test and demonstrate the analytical figures of merit of a femtosecond-laser ablation (fs-LA) system coupled with an inductively coupled plasma-multi-ion collector-mass spectrometer (ICP-MIC-MS). The mobile fs-LA sampling system was designed and assembled at Ames Laboratory and shipped to Oak Ridge National Laboratory (ORNL), where it was integrated with an ICP-MIC-MS. The test period of the integrated systems was February 2-6, 2009. Spatially-resolved analysis of particulate samples is accomplished by 100-shot laser ablation using a fs-pulsewidth laser and monitoring selected isotopes in the resulting ICP-MS transient signal. The capability of performing high sensitivity, spatiallymore » resolved, isotopic analyses with high accuracy and precision and with virtually no sample preparation makes fs-LA-ICP-MIC-MS valuable for the measurement of actinide isotopes at low concentrations in very small samples for nonproliferation purposes. Femtosecond-LA has been shown to generate particles from the sample that are more representative of the bulk composition, thereby minimizing weaknesses encountered in previous work using nanosecond-LA (ns-LA). The improvement of fs- over ns-LA sampling arises from the different mechanisms for transfer of energy into the sample in these two laser pulse-length regimes. The shorter duration fs-LA pulses induce less heating and cause less damage to the sample than the longer ns pulses. This results in better stoichiometric sampling (i.e., a closer correlation between the composition of the ablated particles and that of the original solid sample), which improves accuracy for both intra- and inter-elemental analysis. The primary samples analyzed in this work are (a) solid uranium oxide powdered samples having different {sup 235}U to {sup 238}U concentration ratios, and (b) glass reference materials (NIST 610, 612, 614, and 616). Solid uranium oxide samples containing {sup 235}U in depleted, natural, and enriched abundances were analyzed as particle aggregates immobilized in a collodion substrate. The uranium oxide samples were nuclear reference materials (CRMs U0002, U005-A, 129-A, U015, U030-A, and U050) obtained from New Brunswick Laboratory-USDOE.« less

Fourier Transform Infrared (FT-IR) and Laser Ablation Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) Imaging of Cerebral Ischemia: Combined Analysis of Rat Brain Thin Cuts Toward Improved Tissue Classification.

PubMed

Balbekova, Anna; Lohninger, Hans; van Tilborg, Geralda A F; Dijkhuizen, Rick M; Bonta, Maximilian; Limbeck, Andreas; Lendl, Bernhard; Al-Saad, Khalid A; Ali, Mohamed; Celikic, Minja; Ofner, Johannes

2018-02-01

Microspectroscopic techniques are widely used to complement histological studies. Due to recent developments in the field of chemical imaging, combined chemical analysis has become attractive. This technique facilitates a deepened analysis compared to single techniques or side-by-side analysis. In this study, rat brains harvested one week after induction of photothrombotic stroke were investigated. Adjacent thin cuts from rats' brains were imaged using Fourier transform infrared (FT-IR) microspectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The LA-ICP-MS data were normalized using an internal standard (a thin gold layer). The acquired hyperspectral data cubes were fused and subjected to multivariate analysis. Brain regions affected by stroke as well as unaffected gray and white matter were identified and classified using a model based on either partial least squares discriminant analysis (PLS-DA) or random decision forest (RDF) algorithms. The RDF algorithm demonstrated the best results for classification. Improved classification was observed in the case of fused data in comparison to individual data sets (either FT-IR or LA-ICP-MS). Variable importance analysis demonstrated that both molecular and elemental content contribute to the improved RDF classification. Univariate spectral analysis identified biochemical properties of the assigned tissue types. Classification of multisensor hyperspectral data sets using an RDF algorithm allows access to a novel and in-depth understanding of biochemical processes and solid chemical allocation of different brain regions.

Application of 1013 ohm Faraday cup current amplifiers for boron isotopic analyses by solution mode and laser ablation multicollector inductively coupled plasma mass spectrometry.

PubMed

Lloyd, Nicholas S; Sadekov, Aleksey Yu; Misra, Sambuddha

2018-01-15

Boron isotope ratios (δ 11 B values) are used as a proxy for seawater paleo-pH, amongst several other applications. The analytical precision can be limited by the detection of low intensity ion beams from limited sample amounts. High-gain amplifiers offer improvements in signal/noise ratio and can be used to increase measurement precision and reduce sample amounts. 10 13 ohm amplifier technology has previously been applied to several radiogenic systems, but has thus far not been applied to non-traditional stable isotopes. Here we apply 10 13 ohm amplifier technology for the measurement of boron isotope ratios using solution mode MC-ICP-MS and laser ablation mode (LA-)MC-ICP-MS techniques. Precision is shown for reference materials as well as for low-volume foraminifera samples. The baseline uncertainty for a 0.1 pA 10 B + ion beam is reduced to <0.1 ‰ for a typical measurement period. The external precision is better than 0.2 ‰ (2SD) for δ 11 B measurements for solution samples containing as little as 0.8 ng total boron. For in situ microanalyses with LA-MC-ICP-MS, the external precision of 11 B/ 10 B from an in-house calcite standard was 1 ‰ (2SD) for individual spot analyses, and 0.3 ‰ for the mean of ≥10 replicate spot analyses. 10 13 ohm amplifier technology is demonstrated to offer advantages for the determination of δ 11 B values by both MC-ICP-MS and LA-MC-ICP-MS for small samples of biogenic carbonates, such as foraminifera shells. 10 13 ohm amplifier technology will also be of benefit to other non-traditional stable isotope measurements. Copyright © 2017 John Wiley & Sons, Ltd.

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

NASA Astrophysics Data System (ADS)

Ridley, W. I.

2003-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-02-01

Detection and sourcing of counterfeit currency, examination of counterfeit security documents and determination of authenticity of medical records are examples of common forensic document investigations. In these cases, the physical and chemical composition of the ink entries can provide important information for the assessment of the authenticity of the document or for making inferences about common source. Previous results reported by our group have demonstrated that elemental analysis, using either Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) or Laser Ablation Induced Breakdown Spectroscopy (LIBS), provides an effective, practical and robust technique for the discrimination of document substrates and writing inks with minimal damage to the document. In this study, laser-based methods and Scanning Electron Microscopy-Energy Dispersive X-Ray Spectroscopy (SEM-EDS) methods were developed, optimized and validated for the forensic analysis of more complex inks such as toners and inkjets, to determine if their elemental composition can differentiate documents printed from different sources and to associate documents that originated from the same printing source. Comparison of the performance of each of these methods is presented, including the analytical figures of merit, discrimination capability and error rates. Different calibration strategies resulting in semi-quantitative and qualitative analysis, comparison methods (match criteria) and data analysis and interpretation tools were also developed. A total of 27 black laser toners originating from different manufacturing sources and/or batches were examined to evaluate the discrimination capability of each method. The results suggest that SEM-EDS offers relatively poor discrimination capability for this set (~ 70.7% discrimination of all the possible comparison pairs or a 29.3% type II error rate). Nonetheless, SEM-EDS can still be used as a complementary method of analysis since it has the advantage of being non-destructive to the sample in addition to providing imaging capabilities to further characterize toner samples by their particle morphology. Laser sampling methods resulted in an improvement of the discrimination between different sources with LIBS producing 89% discrimination and LA-ICP-MS resulting in 100% discrimination. In addition, a set of 21 black inkjet samples was examined by each method. The results show that SEM-EDS is not appropriate for inkjet examinations since their elemental composition is typically below the detection capabilities with only sulfur detected in this set, providing only 47.4% discrimination between possible comparison pairs. Laser sampling methods were shown to provide discrimination greater than 94% for this same inkjet set with false exclusion and false inclusion rates lower than 4.1% and 5.7%, for LA-ICP-MS and LIBS respectively. Overall these results confirmed the utility of the examination of printed documents by laser-based micro-spectrochemical methods. SEM-EDS analysis of toners produced a limited utility for discrimination within sources but was not an effective tool for inkjet ink discrimination. Both LA-ICP-MS and LIBS can be used in forensic laboratories to chemically characterize inks on documents and to complement the information obtained by conventional methods and enhance their evidential value.

Improved Precision and Accuracy of Quantification of Rare Earth Element Abundances via Medium-Resolution LA-ICP-MS.

PubMed

Funderburg, Rebecca; Arevalo, Ricardo; Locmelis, Marek; Adachi, Tomoko

2017-11-01

Laser ablation ICP-MS enables streamlined, high-sensitivity measurements of rare earth element (REE) abundances in geological materials. However, many REE isotope mass stations are plagued by isobaric interferences, particularly from diatomic oxides and argides. In this study, we compare REE abundances quantitated from mass spectra collected with low-resolution (m/Δm = 300 at 5% peak height) and medium-resolution (m/Δm = 2500) mass discrimination. A wide array of geological samples was analyzed, including USGS and NIST glasses ranging from mafic to felsic in composition, with NIST 610 employed as the bracketing calibrating reference material. The medium-resolution REE analyses are shown to be significantly more accurate and precise (at the 95% confidence level) than low-resolution analyses, particularly in samples characterized by low (<μg/g levels) REE abundances. A list of preferred mass stations that are least susceptible to isobaric interferences is reported. These findings impact the reliability of REE abundances derived from LA-ICP-MS methods, particularly those relying on mass analyzers that do not offer tuneable mass-resolution and/or collision cell technologies that can reduce oxide and/or argide formation. Graphical Abstract ᅟ.

Improved Precision and Accuracy of Quantification of Rare Earth Element Abundances via Medium-Resolution LA-ICP-MS

NASA Astrophysics Data System (ADS)

Funderburg, Rebecca; Arevalo, Ricardo; Locmelis, Marek; Adachi, Tomoko

2017-07-01

Laser ablation ICP-MS enables streamlined, high-sensitivity measurements of rare earth element (REE) abundances in geological materials. However, many REE isotope mass stations are plagued by isobaric interferences, particularly from diatomic oxides and argides. In this study, we compare REE abundances quantitated from mass spectra collected with low-resolution (m/Δm = 300 at 5% peak height) and medium-resolution (m/Δm = 2500) mass discrimination. A wide array of geological samples was analyzed, including USGS and NIST glasses ranging from mafic to felsic in composition, with NIST 610 employed as the bracketing calibrating reference material. The medium-resolution REE analyses are shown to be significantly more accurate and precise (at the 95% confidence level) than low-resolution analyses, particularly in samples characterized by low (<μg/g levels) REE abundances. A list of preferred mass stations that are least susceptible to isobaric interferences is reported. These findings impact the reliability of REE abundances derived from LA-ICP-MS methods, particularly those relying on mass analyzers that do not offer tuneable mass-resolution and/or collision cell technologies that can reduce oxide and/or argide formation.

Measurement of longitudinal sulfur isotopic variations by laser ablation MC-ICP-MS in single human hair strands.

PubMed

Santamaria-Fernandez, Rebeca; Giner Martínez-Sierra, Justo; Marchante-Gayón, J M; García-Alonso, J Ignacio; Hearn, Ruth

2009-05-01

A new method for the measurement of longitudinal variations of sulfur isotope amount ratios in single hair strands using a laser ablation system coupled to a multicollector inductively coupled plasma mass spectrometer (LA-MC-ICP-MS) is reported here for the first time. Ablation parameters have been optimized for the measurement of sulfur isotope ratios in scalp human hair strands of 80-120-microm thickness and different washing procedures have been evaluated. The repeatability of the method has been tested and the ability to measure sulfur isotopic variations in 1,000-microm-long hair segments has been evaluated. A horse hair sample previously characterized for carbon and nitrogen isotope ratios in an interlaboratory study has been characterized by LA-MC-ICP-MS to be used as an in-house standard for the bracketing of human hair strands. (34)S/(32)S isotope amount ratios have been measured and corrected for instrumental mass bias adopting the external standardization approach using National Institute of Standards and Technology (NIST) RM8553 and full uncertainty budgets have been calculated using the Kragten approach. Results are reported as both (34)S/(32)S isotope amount ratios and deltaS(V-CDT) values (sulfur isotopic differences relative to a reference sample expressed in the Vienna Canyon Diablo Troilite (V-CDT) scale) calculated using NIST RM8553, NIST RM8554, and NIST RM8556 to anchor results to the V-CDT scale. The main advantage of the new method versus conventional gas source isotope ratio mass spectrometry measurements is that longitudinal variations in sulfur isotope amount ratios can be resolved. Proof of concept is shown with human scalp hair strands from three individuals, two UK residents and one traveler (long periods of time abroad). The method enables monitoring of longitudinal isotope ratio variations in single hair strands. Absolute ratios are reported and delta(34)S(V-CDT) values are plotted for comparison. Slight variations of <1.2 per thousand were detected in the hair strands from UK residents whereas the traveler presented a variation of >5 per thousand. Thus, the measurement of sulfur isotopic variations in hair samples has potential to be an indicator of geographical origin and recent movements and could be used in combination with isotope ratio measurements in water/foodstuffs from different geographical locations to provide important information in nutritional and geographical studies.

Quantitative mapping of elements in basil leaves (Ocimum basilicum) based on cesium concentration and growth period using laser ablation ICP-MS.

PubMed

Ko, Jung Aa; Furuta, Naoki; Lim, Heung Bin

2018-01-01

Quantitative elemental mapping of metallic pollutants in sweet basil was studied by laser ablation (LA)-ICP-MS. For this, the sweet basil was cultivated in Hoagland nutrient solution spiked with 100 and 1000 ng mL -1 of Cs for 10-60 days. Then, the Cs distribution in collected leaves was determined by LA-ICP-MS using lab-synthesized standard pellets based on NIST 1573a tomato leaves. For comparison, S, Ca, and K were also simultaneously determined in this measurement with a 13 C + signal from the leaves as an internal standard. The obtained calibration curves showed linear coefficient of determination (R 2 ) of 0.991 for K and 0.999 for Cs. The concentration of Cs measured in the basil leaves increased with growth period and pollutant concentration, and accumulation followed the order of leaf margin, petiole, midrib, and veins. Although no visible symptom was detected, significant suppression of the growth rate was observed due to the presence of high-concentration Cs. The experimental model demonstrated herein showed potential for studying the influence of radioactive pollutants on plants and other organisms in the food chain. Copyright © 2017 Elsevier Ltd. All rights reserved.

Changes in trace and minor constituents and associated micro-architecture of Montastrea faveolata during time of "stress"

USGS Publications Warehouse

Holmes, C.W.; Buster, N.A.; Sorauf, J.E.; Hudson, J.H.; Kester, C.

2003-01-01

As corals grow, they secrete a calcareous skeleton with the aid of photosynthetic activity of endosymbiotic dinoflagellates. The rate of this secretion varies annually which produces annual bands. Entrapped with the carbonate are trace substances that record the chemistry of the surrounding ocean. Detailing these changes in chemistry requires careful high-resolution sampling. New procedures involving laser ablation inductive couple plasma mass spectroscopy (LA-ICP/MS) provides a unique method that does not involve tedious sample preparation. The La-ICP/MS data for a series of Atlantic corals from Looe Key, U.S. Florida Keys shows an intriguing distribution trace and minor elements whose concentrations are related to reported bleaching events. SEM data from the layers exhibit a change in crystal habit concurrent with the changes in chemistry. These changes reflected the affect of the variable influence of the symbiotic algae on the development of the coral skeleton.

Quantitative bioimaging of p-boronophenylalanine in thin liver tissue sections as a tool for treatment planning in boron neutron capture therapy.

PubMed

Reifschneider, Olga; Schütz, Christian L; Brochhausen, Christoph; Hampel, Gabriele; Ross, Tobias; Sperling, Michael; Karst, Uwe

2015-03-01

An analytical method using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was developed and applied to assess enrichment of 10B-containing p-boronophenylalanine-fructose (BPA-f) and its pharmacokinetic distribution in human tissues after application for boron neutron capture therapy (BNCT). High spatial resolution (50 μm) and limits of detection in the low parts-per-billion range were achieved using a Nd:YAG laser of 213 nm wavelength. External calibration by means of 10B-enriched standards based on whole blood proved to yield precise quantification results. Using this calibration method, quantification of 10B in cancerous and healthy tissue was carried out. Additionally, the distribution of 11B was investigated, providing 10B enrichment in the investigated tissues. Quantitative imaging of 10B by means of LA-ICP-MS was demonstrated as a new option to characterise the efficacy of boron compounds for BNCT.

New procedure of quantitative mapping of Ti and Al released from dental implant and Mg, Ca, Fe, Zn, Cu, Mn as physiological elements in oral mucosa by LA-ICP-MS.

PubMed

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

2017-12-01

A new procedure for determination of elements derived from titanium implants and physiological elements in soft tissues by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is presented. The analytical procedure was developed which involved preparation of in-house matrix matched solid standards with analyte addition based on certified reference material (CRM) MODAS-4 Cormorant Tissue. Addition of gelatin, serving as a binding agent, essentially improved physical properties of standards. Performance of the analytical method was assayed and validated by calculating parameters like precision, detection limits, trueness and recovery of analyte addition using additional CRM - ERM-BB184 Bovine Muscle. Analyte addition was additionally confirmed by microwave digestion of solid standards and analysis by solution nebulization ICP-MS. The detection limits are in range 1.8μgg -1 to 450μgg -1 for Mn and Ca respectively. The precision values range from 7.3% to 42% for Al and Zn respectively. The estimated recoveries of analyte addition line within scope of 83%-153% for Mn and Cu respectively. Oral mucosa samples taken from patients treated with titanium dental implants were examined using developed analytical method. Standards and tissue samples were cryocut into 30µm thin sections. LA-ICP-MS allowed to obtain two-dimensional maps of distribution of elements in tested samples which revealed high content of Ti and Al derived from implants. Photographs from optical microscope displayed numerous particles with µm size in oral mucosa samples which suggests that they are residues from implantation procedure. Copyright © 2017 Elsevier B.V. All rights reserved.

Foraminiferal Stable Isotope Geochemistry At The Micrometer Scale: Is It A Dream Or Reality?

NASA Astrophysics Data System (ADS)

Misra, S.; Shuttleworth, S.; Lloyd, N. S.; Sadekov, A.; Elderfield, H.

2012-12-01

Over last few decades trace metals and stable isotope compositions of foraminiferal shells became one of the major tools to study past oceans and associated climate change. Empirical calibrations of δ11B, δ18O, Mg/Ca, Cd/Ca, Ba/Ca shells compositions have linked them to various environmental parameters such as seawater pH, temperature, salinity and productivity. Despite their common use as proxies, little is known about mechanisms of trace metals incorporation into foraminiferal calcite. Trace metals partition coefficients for foraminiferal calcite is significantly different from inorganic calcite precipitates underlining strong biological control on metal transport to the calcification sites and their incorporation into the calcite. Microscale distribution of light elements isotopes (e.g. Li, B, Mg) could potentially provide unique inside into these biomineralization processes improving our understanding of foraminiferal geochemistry. In this work we explore potentials of using recent advances in analytical geochemistry by employing laser ablation and multi-collector ICP-MS to study microscale distribution of Mg isotopes across individual foraminiferal shells and δ11B, and δ7Li analyses of individual shell chambers. The analytical setup includes an Analyte.G2 193nm excimer laser ablation system with two volume ablation cell connected to a Thermo Scientific NEPTUNE Plus MC-ICP-MS with Jet Interface option. We will discuss method limitations and advantages for foraminiferal geochemistry as well as our data on Mg isotopes distribution within shells of planktonic foraminifera.

A matrix effect and accuracy evaluation for the determination of elements in milk powder LIBS and laser ablation/ICP-OES spectrometry.

PubMed

Gilon, N; El-Haddad, J; Stankova, A; Lei, W; Ma, Q; Motto-Ros, V; Yu, J

2011-11-01

Laser ablation coupled to inductively coupled plasma optical emission spectrometry (LA-ICP-OES) and laser-induced breakdown spectroscopy (LIBS) were investigated for the determination of Ca, Mg, Zn and Na in milk samples. The accuracy of both methods was evaluated by comparison of the concentration found using LA-ICP-OES and LIBS with classical wet digestion associated with ICP-OES determination. The results were not fully acceptable, with biases from less than 1% to more than 60%. Matrix effects were also investigated. The sample matrix can influence the temperature, electron number density (n (e)) and other excitation characteristics in the ICP. These ICP characteristics were studied and evaluated during ablation of eight milk samples. Differences in n (e) (from 8.9 to 13.8 × 10(14) cm(-3)) and rotational temperature (ranging from 3,400 to 4,400 K) occurred with no correlation with trueness. LIBS results obtained after classical external calibration procedure gave degraded accuracy, indicating a strong matrix effect. The LIBS measurements clearly showed that the major problem in LA-ICP was related to the ablation process and that LIBS spectroscopy is an excellent diagnostic tool for LA-ICP techniques.

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

PubMed

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

2013-03-01

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

Characterization and forensic analysis of soil samples using laser-induced breakdown spectroscopy (LIBS).

PubMed

Jantzi, Sarah C; Almirall, José R

2011-07-01

A method for the quantitative elemental analysis of surface soil samples using laser-induced breakdown spectroscopy (LIBS) was developed and applied to the analysis of bulk soil samples for discrimination between specimens. The use of a 266 nm laser for LIBS analysis is reported for the first time in forensic soil analysis. Optimization of the LIBS method is discussed, and the results compared favorably to a laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) method previously developed. Precision for both methods was <10% for most elements. LIBS limits of detection were <33 ppm and bias <40% for most elements. In a proof of principle study, the LIBS method successfully discriminated samples from two different sites in Dade County, FL. Analysis of variance, Tukey's post hoc test and Student's t test resulted in 100% discrimination with no type I or type II errors. Principal components analysis (PCA) resulted in clear groupings of the two sites. A correct classification rate of 99.4% was obtained with linear discriminant analysis using leave-one-out validation. Similar results were obtained when the same samples were analyzed by LA-ICP-MS, showing that LIBS can provide similar information to LA-ICP-MS. In a forensic sampling/spatial heterogeneity study, the variation between sites, between sub-plots, between samples and within samples was examined on three similar Dade sites. The closer the sampling locations, the closer the grouping on a PCA plot and the higher the misclassification rate. These results underscore the importance of careful sampling for geographic site characterization.

Intra- and inter-tooth variation in strontium isotope ratios from prehistoric seals by laser ablation (LA)-MC-ICP-MS.

PubMed

Glykou, A; Eriksson, G; Storå, J; Schmitt, M; Kooijman, E; Lidén, K

2018-05-04

Strontium isotope ratios ( 87 Sr/ 86 Sr) in modern-day marine environments are considered to be homogeneous (~0.7092). However, in the Baltic Sea, the Sr ratios are controlled by mixing seawater and continental drainage from major rivers discharging into the Baltic. This pilot study explores if variations in Sr can be detected in marine mammals from archaeological sites in the Baltic Sea. 87 Sr/ 86 Sr ratios were measured in tooth enamel from three seal species by laser ablation (LA)-MC-ICP-MS. The method enables micro-sampling of solid materials. This is the first time that the method has been applied to marine samples from archaeological collections. The analyses showed inter-tooth 87 Sr/ 86 Sr variation suggesting that different ratios can be detected in different regions of the Baltic Sea. Furthermore, the intra-tooth variation suggests possible different geographic origin or seasonal movement of seals within different regions in the Baltic Sea through their life time. The method was successfully applied to archaeological marine samples showing that: (1) the 87 Sr/ 86 Sr ivalue n marine environments is not uniform, (2) 87 Sr/ 86 Sr differences might reflect differences in ecology and life history of different seal species, and (3) archaeological mobility studies based on 87 Sr/ 86 Sr ratio in humans should therefore be evaluated together with diet reconstruction. This article is protected by copyright. All rights reserved.

Development of dried serum spot sampling techniques for the assessment of trace elements in serum samples by LA-ICP-MS.

PubMed

Chantada-Vázquez, María Pilar; Moreda-Piñeiro, Jorge; Cantarero-Roldán, Alicia; Bermejo-Barrera, Pilar; Moreda-Piñeiro, Antonio

2018-08-15

A novel approach for serum analysis by dried matrix spot (DMS) technique is proposed. The methodology consists of sampling filter paper discs (2.7 mm in diameter) containing the large amount of serum retained after a single spotting. Several oxidizers (sodium chlorate, sodium azide, acetic acid, formic acid, 1-butyl-3-methylimidazoliumm chloride/bromide) were tested (oxidizers premixed with the sample before spotting, and papers previously soaked in concentrated additive/oxidizer solutions). Direct multi-element determination (Al, Be, Ca, Cu, Fe, K, Li, Mg, Mn, Mo, Na, P, Rb, Se, V, and Zn) in dried serum spots at very low levels was therefore assessed by laser ablation (LA) coupled with inductively coupled plasma - mass spectrometry (ICP-MS). Laser ablation was performed using a focused Nd: YAG laser beam in lineal scan mode (wavelength 213 nm, laser fluency 2.2 J cm -2 , repetition rate 20 Hz, laser spot diameter 90 µm, depth 0 µm, scanning speed 12 µm s -1 ). Matrix-matched calibration mode and 13 C as internal standard (for signal intensities normalization) was used throughout the work. Limits of quantification were found to be from 21 µg L -1 to 221 mg L -1 . Repeatability (seven ablations of the same dried serum spot) and reproducibility (two ablations of seven dried serum spot from the same material) offered RSDs below 12% for all analytes, which seems satisfactory for clinical purposes. The method was validated by analyzing several certified reference materials (Seronorm™ level I and II trace elements in serum), and it was applied to several DMS from serum samples from healthy adults. Copyright © 2018 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

Peters, Daniel; Pettke, Thomas

2016-04-01

An efficient, clean procedure for bulk rock major to trace element analysis by 193 nm Excimer LA-ICP-MS analysis of nanoparticulate pressed powder pellets (PPPs) employing a binder is presented. Sample powders are milled in water suspension in a planetary ball mill, reducing average grain size by about one order of magnitude compared to common dry milling protocols. Microcrystalline cellulose (MCC) is employed as a binder, improving the mechanical strength of the PPP and the ablation behaviour, because MCC absorbs 193 nm laser light well. Use of MCC binder allows for producing cohesive pellets of materials that cannot be pelletized in their pure forms, such as quartz powder. Rigorous blank quantification was performed on synthetic quartz treated like rock samples, demonstrating that procedural blanks are irrelevant except for a few elements at the 10 ng g-1 concentration level. The LA-ICP-MS PPP analytical procedure was optimised and evaluated using six different SRM powders (JP-1, UB-N, BCR-2, GSP-2, OKUM, and MUH-1). Calibration based on external standardization using SRM 610, SRM 612, BCR-2G, and GSD-1G glasses allows for evaluation of possible matrix effects during LA-ICP-MS analysis. The data accuracy of the PPP LA-ICP-MS analytical procedure compares well to that achieved for liquid ICP-MS and LA-ICP-MS glass analysis, except for element concentrations below ˜30 ng g-1, where liquid ICP-MS offers more precise data and in part lower limits of detection. Uncertainties on the external reproducibility of LA-ICP-MS PPP element concentrations are of the order of 0.5 to 2 % (1σ standard deviation) for concentrations exceeding ˜1 μg g-1. For lower element concentrations these uncertainties increase to 5-10% or higher when analyte-depending limits of detection (LOD) are approached, and LODs do not significantly differ from glass analysis. Sample homogeneity is demonstrated by the high analytical precision, except for very few elements where grain size effects can rarely still be resolved analytically. Matrix effects are demonstrated for PPP analysis of diverse rock compositions and basalt glass analysis when externally calibrated based on SRM 610 and SRM 612 glasses; employing basalt glass GSD-1G or BCR-2G for external standardisation basically eliminates these problems. Perhaps the most prominent progress of the LA-ICP-MS PPP analytical procedure presented here is the fact that trace elements not commonly analysed, i.e. new, unconventional geochemical tracers, can be measured straightforwardly, including volatile elements, the flux elements Li and B, the chalcophile elements As, Sb, Tl, Bi, and elements that alloy with metal containers employed in conventional glass production approaches. The method presented here thus overcomes many common problems and limitations in analytical geochemistry and is shown to be an efficient alternative for bulk rock trace elements analysis.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Galiova, Michaela; Kaiser, Jozef; Fortes, Francisco 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 themore » 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.« less

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

PubMed

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

2016-03-10

The sulfur isotope is an important geochemical tracer in diverse fields of geosciences. In this study, the effects of three different cone combinations with the addition of N2 on the performance of in situ S isotope analyses were investigated in detail. The signal intensities of S isotopes were improved by a factor of 2.3 and 3.6 using the X skimmer cone combined with the standard sample cone or the Jet sample cone, respectively, compared with the standard arrangement (H skimmer cone combined with the standard sample cone). This signal enhancement is important for the improvement of the precision and accuracy of in situ S isotope analysis at high spatial resolution. Different cone combinations have a significant effect on the mass bias and mass bias stability for S isotopes. Poor precisions of S isotope ratios were obtained using the Jet and X cones combination at their corresponding optimum makeup gas flow when using Ar plasma only. The addition of 4-8 ml min(-1) nitrogen to the central gas flow in laser ablation MC-ICP-MS was found to significantly enlarge the mass bias stability zone at their corresponding optimum makeup gas flow in these three different cone combinations. The polyatomic interferences of OO, SH, OOH were also significantly reduced, and the interference free plateaus of sulfur isotopes became broader and flatter in the nitrogen mode (N2 = 4 ml min(-1)). However, the signal intensity of S was not increased by the addition of nitrogen in this study. The laser fluence and ablation mode had significant effects on sulfur isotope fractionation during the analysis of sulfides and elemental sulfur by laser ablation MC-ICP-MS. The matrix effect among different sulfides and elemental sulfur was observed, but could be significantly reduced by line scan ablation in preference to single spot ablation under the optimized fluence. It is recommended that the d90 values of the particles in pressed powder pellets for accurate and precise S isotope analysis should be less than 10 μm. Under the selected optimized analytical conditions, excellent agreements between the determined values and the reference values were achieved for the IAEA-S series standard reference materials and a set of six well-characterized, isotopic homogeneous sulfide standards (PPP-1, MoS2, MASS-1, P-GBW07267, P-GBW07268, P-GBW07270), validating the capability of the developed method for providing high-quality in situ S isotope data in sulfides and elemental sulfur. Copyright © 2016. Published by Elsevier B.V.

Bioimaging of isosteric osmium and ruthenium anticancer agents by LA-ICP-MS.

PubMed

Klose, Matthias H M; Theiner, Sarah; Kornauth, Christoph; Meier-Menches, Samuel M; Heffeter, Petra; Berger, Walter; Koellensperger, Gunda; Keppler, Bernhard K

2018-03-01

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to study the spatial distribution of two metallodrugs with anticancer activities in vivo, namely the organoruthenium plecstatin-1 (1) and its isosteric osmium analogue (2), in liver, kidneys, muscles and tumours of treated mice bearing a CT-26 tumour after single-dose i.p. administration. To the best of our knowledge, this is the first time that the spatial distribution of an osmium drug candidate has been investigated using LA-ICP-MS in tissues. Independent measurements of the average ruthenium and osmium concentration via microwave digestion and ICP-MS in organs and tumours were in good agreement with the LA-ICP-MS results. Matrix-matched standards (MMS) ranging from 1 to 30 μg g -1 were prepared to quantify the spatial distributions of the metals and the average metal content of the MMS samples was additionally quantified by ICP-MS after microwave digestion. The recoveries for osmium and ruthenium in the MMS were 105% and 101% on average, respectively, validating the sample preparation procedure of the MMS. Preparation of MMS was carried out under an argon atmosphere to prevent oxidation of osmium-species to the volatile OsO 4 . The highest metal concentrations were found in the liver, followed by kidney, lung and tumour tissues, while muscles displayed only very low quantities of the respective metal. Both metallodrugs accumulated in the cortex of the kidneys more strongly compared to the medulla. Interestingly, osmium from 2 was largely located at the periphery and tissue edges, whereas ruthenium from 1 was observed to penetrate deeper into the organs and tumours.

Micro-scale novel stable isotope fractionation during weathering disclosed by femtosecond laser ablation

NASA Astrophysics Data System (ADS)

Schuessler, J. A.; von Blanckenburg, F.

2012-12-01

The stable isotope fractionation of metals and metalloids during chemical weathering and alteration of rocks at low temperature is a topic receiving increasing scientific attention. For these systems, weathering of primary minerals leads to selective partitioning of isotopes between the secondary minerals formed from them, and the dissolved phase of soil or river water. While the isotopic signatures of these processes have been mapped-out at the catchment or the soil scale, the actual isotopic fractionation is occurring at the mineral scale. To identify the processes underlying such micro-scale fractionation, the development of micro-analytical tools allows to investigate mechanisms of isotope fractionation in-situ, in combination with textural information of weathering reactions. We have developed a second-generation UV femtosecond (fs) laser system at GFZ Potsdam. The advantage of UV-fs laser ablation is the reduction of laser-induced isotopic and elemental fractionation by avoiding 'thermal effects' during ablation, such that accurate isotope ratios can be measured by standard-sample-standard bracketing using laser ablation multicollector ICP-MS; where the matrix of the bracketing standard does not need to match that of the sample [1]. Our system consists of the latest generation femtosecond solid-state laser (Newport Spectra Physics Solstice), producing an ultra short pulse width of about 100 femtoseconds at a wavelength of 196 nm. The system is combined with a custom-build computer-controlled sample stage and allows fully automated isotope analyses through synchronised operation of the laser with the Neptune MC-ICP-MS. To assess precision and accuracy of our laser ablation method, we analysed various geological reference materials. We obtained δ30Si values of -0.31 ± 0.23 (2SD, n = 13) for basalt glass BHVO-2G, and -1.25 ± 0.21 (2SD, n = 27) for pure Si IRMM17 when bracketed against NBS-28 quartz. δ56Fe and δ26Mg values obtained from non-matrix matched standard-sample-bracketing laser ablation analyses on sulfides, oxides and silicates agree within 0.15 permil to measurements done by solution MC-ICP-MS after chromatographic matrix separation. With our laser ablation method all compartments of the weathering zone can be analysed with minimal sample preparation [2]. In a first application, we investigate Si isotope fractionation during deep (10 m) core stone weathering, where crystalline rock is altered, producing secondary clay minerals along 20 micrometer wide (biogenic?) alteration textures. While unweathered centers of plagioclase grains show a homogenous Si isotope composition of δ30Si = -0.20 ± 0.17 permil (2SD, n=12), the secondary weathering products found in fissures within and between plagioclase grains consistently show negative δ30Si values - as low as -1.13 permil. Comparison with isotope studies at the soil and catchment scale suggests that the isotopic weathering signatures found in dissolved and particulate Si in rivers can be traced to processes operating at the micro scale. [1] Horn & von Blanckenburg, Spectrochimica Acta B. 62, 2007 [2] Steinhoefel et al., Chem. Geol. 286, 2011

Percolation Diffusion into Self-Assembled Mesoporous Silica Microfibres

PubMed Central

Canning, John; Huyang, George; Ma, Miles; Beavis, Alison; Bishop, David; Cook, Kevin; McDonagh, Andrew; Shi, Dongqi; Peng, Gang-Ding; Crossley, Maxwell J.

2014-01-01

Percolation diffusion into long (11.5 cm) self-assembled, ordered mesoporous microfibres is studied using optical transmission and laser ablation inductive coupled mass spectrometry (LA-ICP-MS). Optical transmission based diffusion studies reveal rapid penetration (<5 s, D > 80 μm2∙s−1) of Rhodamine B with very little percolation of larger molecules such as zinc tetraphenylporphyrin (ZnTPP) observed under similar loading conditions. The failure of ZnTPP to enter the microfibre was confirmed, in higher resolution, using LA-ICP-MS. In the latter case, LA-ICP-MS was used to determine the diffusion of zinc acetate dihydrate, D~3 × 10−4 nm2∙s−1. The large differences between the molecules are accounted for by proposing ordered solvent and structure assisted accelerated diffusion of the Rhodamine B based on its hydrophilicity relative to the zinc compounds. The broader implications and applications for filtration, molecular sieves and a range of devices and uses are described. PMID:28348290

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

NASA Technical Reports Server (NTRS)

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

2008-01-01

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

Method validation for simultaneous determination of chromium, molybdenum and selenium in infant formulas by ICP-OES and ICP-MS.

PubMed

Khan, Naeem; Jeong, In Seon; Hwang, In Min; Kim, Jae Sung; Choi, Sung Hwa; Nho, Eun Yeong; Choi, Ji Yeon; Kwak, Byung-Man; Ahn, Jang-Hyuk; Yoon, Taehyung; Kim, Kyong Su

2013-12-15

This study aimed to validate the analytical method for simultaneous determination of chromium (Cr), molybdenum (Mo), and selenium (Se) in infant formulas available in South Korea. Various digestion methods of dry-ashing, wet-digestion and microwave were evaluated for samples preparation and both inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS) were compared for analysis. The analytical techniques were validated by detection limits, precision, accuracy and recovery experiments. Results showed that wet-digestion and microwave methods were giving satisfactory results for sample preparation, while ICP-MS was found more sensitive and effective technique than ICP-OES. The recovery (%) of Se, Mo and Cr by ICP-OES were 40.9, 109.4 and 0, compared to 99.1, 98.7 and 98.4, respectively by ICP-MS. The contents of Cr, Mo and Se in infant formulas by ICP-MS were found in good nutritional values in accordance to nutrient standards for infant formulas CODEX values. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

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

PubMed

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

2016-01-01

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

Trace analysis of high-purity graphite by LA-ICP-MS.

PubMed

Pickhardt, C; Becker, J S

2001-07-01

Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been established as a very efficient and sensitive technique for the direct analysis of solids. In this work the capability of LA-ICP-MS was investigated for determination of trace elements in high-purity graphite. Synthetic laboratory standards with a graphite matrix were prepared for the purpose of quantifying the analytical results. Doped trace elements, concentration 0.5 microg g(-1), in a laboratory standard were determined with an accuracy of 1% to +/- 7% and a relative standard deviation (RSD) of 2-13%. Solution-based calibration was also used for quantitative analysis of high-purity graphite. It was found that such calibration led to analytical results for trace-element determination in graphite with accuracy similar to that obtained by use of synthetic laboratory standards for quantification of analytical results. Results from quantitative determination of trace impurities in a real reactor-graphite sample, using both quantification approaches, were in good agreement. Detection limits for all elements of interest were determined in the low ng g(-1) concentration range. Improvement of detection limits by a factor of 10 was achieved for analyses of high-purity graphite with LA-ICP-MS under wet plasma conditions, because the lower background signal and increased element sensitivity.

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

PubMed

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

2015-05-01

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

Investigation of Cu-, Zn- and Fe-containing human brain proteins using isotopic-enriched tracers by LA-ICP-MS and MALDI-FT-ICR-MS

NASA Astrophysics Data System (ADS)

Becker, J. Susanne; Zoriy, Miroslav; Pickhardt, Carola; Przybylski, Michael; Becker, J. Sabine

2005-04-01

Identification of metal-containing proteins and determination of Cu, Fe, Zn concentration in very small protein volumes is of increasing importance in protein research. Proteins containing metal ions were analyzed directly and simultaneously in separated protein spots in two-dimensional gels (2D gels) by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as an element mass spectrometric technique. In order to study the formation of proteins containing Cu, Zn and Fe in a human brain sample, isotopic-enriched tracers (54Fe, 65Cu and 67Zn) were doped to two-dimensional gels of separated Alzheimer-diseased brain proteins after two-dimensional (2D) gel electrophoresis. The protein spots were screened systematically by LA-ICP-MS with respect to these metal ion intensities. 54Fe/56Fe, 65Cu/63Cu and 67Zn/64Zn isotope ratios in metal-containing proteins were measured directly by LA-ICP-MS. The isotope ratio measurements obtained by LA-ICP-MS indicate certain protein spots with a natural isotope composition of Cu, Zn and/or Fe. These proteins already contained the metal investigated in the original proteins and are stable enough to survive the reducing conditions during gel electrophoresis. On the other hand, proteins with a changed isotope ratio of metals in comparison to the isotope ratio in nature demonstrate the accumulation of tracers within the protein complexes during the tracer experiments in 2D gels. The identification of singular protein spots from Alzheimer-diseased brain separated by 2D gel electrophoresis was attempted by biopolymer mass spectrometry using MALDI-FTICR-MS after excision from the 2D gel and tryptic digestion.

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

DTIC Science & Technology

2008-11-03

Ecstall pluton in the Coast Mountains of British Columbia: Evidence for local deformation rather than large-scale transport. Journal of Geophysical...Journal of Metamorphic Geology 18, 719–735. Kalsbeek, F., Jepsen, H.F., Nutman, A.P., 2001. From source migmatites to plutons : tracking the origin of

A Henry's Law Test for Experimental Partitioning Studies of Iron Meteorites

NASA Technical Reports Server (NTRS)

Chabot, N. L.; Campbell, A. J.; Humayun, M.; Agee, C. B.

2001-01-01

Low-level doped solid metal/liquid metal experiments analyzed by laser ablation ICP-MS allow Henry's Law to be tested. The results indicate Henry's Law is obeyed and the experimental partition coefficients can be applied to iron meteorites. Additional information is contained in the original extended abstract.

Whale baleen trace element signatures: a predictor of environmental life history?

NASA Astrophysics Data System (ADS)

Wilcox Freeburg, E.; Brault, S.; Mayo, C.; Oktay, S.; Hannigan, R.

2009-12-01

The analysis of trace element composition of biogenic structures (e.g., otoliths, feathers) by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) provides unique insights into the environmental life history of individuals. We studied the trace element chemistry of right whale baleens in an attempt to reconstruct migration patterns. Though much is known about the feeding and breeding habitats of these whales, little is known about the location in which they spend most of their adult years. Baleens, made of keratin, grow continuously and are metabolically inactive. Previous work showed that the stable isotope chemistry along the length of a baleen records changes in diet, such as weaning. Baleen chemistry should, therefore, also record the environmental life history of the individual. Trace metal chemistry along a single baleen plate from a right whale were analyzed by LA-ICP-MS. Semi-quantitative elemental signatures were obtained using NIST 612 (glass standard) and MACS-3 (calcium carbonate standard). These concentrations were then compared for accuracy to acid digested baleen laterally adjacent to the laser ablation site via aqueous ICP-MS. Elemental chemistry was compared to known feeding/breeding locations of the individual (water chemistry). Using these comparisons as well as principal components analysis, life history of the individual was reconstructed. Development of an in-house keratin standard is in progress and is expected to strengthen the confidence in results. Future work is expected to bring a more complete knowledge of right whale wintering habits.

Microbeam Characterization of Corning Archeological Reference Glasses: New Additions to the Smithsonian Microbeam Standard Collection

PubMed Central

Vicenzi, Edward P.; Eggins, Stephen; Logan, Amelia; Wysoczanski, Richard

2002-01-01

An initial study of the minor element, trace element, and impurities in Corning archeological references glasses have been performed using three microbeam techniques: electron probe microanalysis (EPMA), laser ablation ICP-mass spectrometry (LA ICP-MS), and secondary ion mass spectrometry (SIMS). The EPMA results suggest a significant level of heterogeneity for a number of metals. Conversely, higher precision and a larger sampling volume analysis by LA ICP-MS indicates a high degree of chemical uniformity within all glasses, typically <2 % relative (1 σ). SIMS data reveal that small but measurable quantities of volatile impurities are present in the glasses, including H at roughly the 0.0001 mass fraction level. These glasses show promise for use as secondary standards for minor and trace element analyses of insulating materials such as synthetic ceramics, minerals, and silicate glasses. PMID:27446764

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grate, Jay W.; Bliss, Mary; Farmer, Orville T.

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

Isotopic and elemental analysis of fish tissues for provenance determination

NASA Astrophysics Data System (ADS)

Zannella, Carmela; Adamo, Paola; Opper, Christine; Schwendinger, Susanne; Knezevic, Sara; Van den Oever, Sabrina; Tchaikovsky, Anastassiya; Zitek, Andreas; Prohaska, Thomas

2017-04-01

The reliable tracing of the productions flows of food products through the entire supply chain is an essential requirement for all types of food commodities qualified by origin, composition and quality. This is a minimum requirement to implement safety for the consumer, enhance consumer confidence and countervail fraudulent practices. One important food commodity is fish and fish products. Reliable methods to trace the origin of fish have become of high importance. The investigation focused on the identification of adequate geochemical marker in fish meat and the corresponding linkage to the ambient water. The Sr/Ca ratio along with the 87Sr/86Sr isotope ratio analyzed by (multi collector) inductively coupled plasma mass spectrometry (MC ICP-MS) proved to be the most potential tools in this respect. For the first time, a direct link of fish meat to water could be accomplished.In addition, fish hard parts (otoliths, fin rays, fish bones) were under investigation to reconstruct the habitat changes during the lifespan of a fishes life. Fish hard parts have the potential to serve as "life time recorder". Thus the spatial investigation of the elemental and isotopic composition can be used to monitor habitat changes with time. The spatially resolved data of hard tissues was collected by means of Laser Ablation Split Stream ICP-MS/MC ICP-MS. This work is accomplished within the scope of the project "CSI: TRACE YOUR FOOD".

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

PubMed Central

Hare, Dominic J.; Kysenius, Kai; Paul, Bence; Knauer, Beate; Hutchinson, Robert W.; O'Connor, Ciaran; Fryer, Fred; Hennessey, Tom P.; Bush, Ashley I.; Crouch, Peter J.; Doble, Philip A.

2017-01-01

Metals are found ubiquitously throughout an organism, with their biological role dictated by both their chemical reactivity and abundance within a specific anatomical region. Within the brain, metals have a highly compartmentalized distribution, depending on the primary function they play within the central nervous system. Imaging the spatial distribution of metals has provided unique insight into the biochemical architecture of the brain, allowing direct correlation between neuroanatomical regions and their known function with regard to metal-dependent processes. In addition, several age-related neurological disorders feature disrupted metal homeostasis, which is often confined to small regions of the brain that are otherwise difficult to analyze. Here, we describe a comprehensive method for quantitatively imaging metals in the mouse brain, using laser ablation - inductively coupled plasma - mass spectrometry (LA-ICP-MS) and specially designed image processing software. Focusing on iron, copper and zinc, which are three of the most abundant and disease-relevant metals within the brain, we describe the essential steps in sample preparation, analysis, quantitative measurements and image processing to produce maps of metal distribution within the low micrometer resolution range. This technique, applicable to any cut tissue section, is capable of demonstrating the highly variable distribution of metals within an organ or system, and can be used to identify changes in metal homeostasis and absolute levels within fine anatomical structures. PMID:28190025

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

A comparison of lead-isotope measurements on exploration-type samples using inductively coupled plasma and thermal ionization mass spectrometry

USGS Publications Warehouse

Gulson, B.L.; Meier, A.L.; Church, S.E.; Mizon, K.J.

1989-01-01

Thermal ionization mass spectrometry (TI-MS) has long been the method of choice for Pb-isotope determinations. More recently, however, inductively coupled plasma mass spectrometry (ICP-MS) has been used to determine Pb-isotope ratios for mineral exploration. The ICP-MS technique, although not as precise as TI-MS, may promote a wider application of Ph-isotope ratio methods because it allows individual isotopes to be determined more rapidly, generally without need for chemical separation (e.g., Smith et al., 1984; Hinners et al., 1987). To demonstrate the utility of the ICP-MS method, we have conducted a series of Pb-isotope measurements on several suites of samples using both TI-MS and ICP-MS. ?? 1989.

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

NASA Astrophysics Data System (ADS)

Guillong, M.; Günther, D.

2001-07-01

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

QEMSCAN+LA-ICP-MS: a 'big data' generator for sedimentary provenance analysis

NASA Astrophysics Data System (ADS)

Vermeesch, Pieter; Rittner, Martin; Garzanti, Eduardo

2017-04-01

Sedimentary provenance may be traced by 'fingerprinting' sediments with chemical, mineralogical or isotopic means. Normally, each of these provenance proxies is characterised on a separate aliquot of the same sample. For example, the chemical composition of the bulk sample may be analysed by X-ray fluorescence (XRF) on one aliquot, framework petrography on another, heavy mineral analysis on a density separate of a third split, and zircon U-Pb dating on a further density separate of the heavy mineral fraction. The labour intensity of this procedure holds back the widespread application of multi-method provenance studies. We here present a new method to solve this problem and avoid mineral separation by coupling a QEMSCAN electron microscope to an LA-ICP-MS instrument and thereby generate all four aforementioned provenance datasets as part of the same workflow. Given a polished hand specimen, a petrographic thin section, or a grain mount, the QEMSCAN+LA-ICP-MS method produces chemical and mineralogical maps from which the X-Y coordinates of the datable mineral are extracted. These coordinates are subsequently passed on to the laser ablation system for isotopic and, hence, geochronological analysis. In the process of finding all the zircons in a sediment grain mount, the QEMSCAN yields the compositional and mineralogical compositions as byproducts. We have applied the new QEMSCAN+LA-ICP-MS instrument suite to over 100 samples from three large sediment routing systems: (1) the Tigris-Euphrates river catchments and Rub' Al Khali desert in Arabia; (2) the Nile catchment in northeast Africa and (3) desert and beach sands between the Orange and Congo rivers in southwest Africa. These studies reveal (1) that Rub' Al Khali sand is predominantly derived from the Arabian Shield and not from Mesopotamia; (2) that the Blue Nile is the principal source of Nile sand; and (3) that Orange River sand is carried northward by longshore drift nearly 1,800km from South Africa to southern Angola. In addition to these geological findings, the first applications of QEMSCAN+LA-ICP-MS highlight some key advantages of the new workflow over traditional provenance analysis: (a) the new method not only increases sample throughput but also improves data quality by reducing significant biases associated with mineral separation and grain selection; (b) the three case studies highlight the importance of zircon 'fertility' for interpreting detrital zircon U-Pb datasets, and the ability of QEMSCAN to quantify this crucial parameter semi-automatically; (c) QEMSCAN+LA-ICP-MS provides an opportunity to add textural information to detrital geochronology and, for example, quantify possible grain-size dependence of U-Pb age distributions. But besides these advantages, the three case studies also reveal a number of limitations: (a) mineral identification by QEMSCAN is not as reliable as commonly achieved by human observers; (b) heavy mineral compositions obtained by QEMSCAN cannot easily be compared with conventional point counting data; and (c) apparent grain sizes can be greatly affected by polishing artefacts. In conclusion, QEMSCAN+LA-ICP-MS is a transformational new technique for provenance analysis but should be used with caution, in combination with conventional petrographic and heavy mineral techniques.

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

NASA Astrophysics Data System (ADS)

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

2012-04-01

Chlorine and bromine are highly conservative elements, and are therefore widely used to trace the origin of fluids in sedimentary and hydrothermal/magmatic systems (e.g. Hanor & McIntosh, 2007; Nahnybida et al., 2009). Halogens are important ligands for metal transport in hydrothermal solutions and thus their behavior in hydrothermal environments is crucial for comprehending ore-forming processes. Besides fluid inclusions, scapolite-group minerals hold great potential as a tracer of igneous, metamorphic, and hydrothermal processes, as no Cl/Br fractionation in scapolite has been observed and therefore halogen ratios in scapolite are thought to mirror the halogen ratios in coexisting melts and fluids (Pan & Dong, 2003). Hence, Cl/Br ratios in fluid inclusions and minerals can be utilized to trace the origin of fluids and fluid-rock interaction pathways. Due to their high ionization energies, bromine and chlorine are not routinely measured by LA-ICP-MS and suitable standards are rare. Little is known about the potential interferences and analytical limitations of in-situ chlorine and bromine analysis by LA-ICP-MS. Nevertheless, Seo et al. (2011) showed that quantification of Br and Cl in single synthetic and natural fluid inclusions is possible. In this study, we have analyzed several scapolite grains of known bromine and chlorine concentrations by LA-ICP-MS and assess the capabilities and limitations of this method. The results show that Cl/Br ratios measured by LA-ICP-MS closely reproduce known values determined by microprobe (Cl), the Noble Gas Method (Br) and INAA (Br) (Kendrick, 2011; Lieftink et al., 1993) using laser ablation spot sizes from 24-120 μm. The well-characterized scapolite grains cover bromine concentrations from 50-883 ppm and chlorine concentrations from 3 to 4 wt.%. In order to further assess the method, we analyzed Cl/Br ratios in natural fluid inclusions hosted in sphalerite that were previously characterized by crush and leach ion chromatography. This is the first time that bulk crush and leach Cl/Br analyses can be compared with Cl/Br ratios within individual fluid inclusions. Our LA-ICP-MS measurements are in good agreement with bulk crush and leach analyses. For instance, molar Cl/Br ratios of single fluid inclusions (183±33) in sphalerite form East Tennessee match those obtained by crush and leach (206±8) Additionally, scapolite in samples from dykes of the Burstall granite, associated banded skarns and metasediments from the Mary Kathleen Fold Belt, Queensland, Australia are being studied. Scapolite is highly luminescent and therefore, cathodoluminescence images resolve chemical zoning in scapolite group minerals that, in combination with in-situ Cl/Br analyses, is a powerful tool to better understand fluid sources and fluid-rock interaction within various geological environments.

Boron detection from blood samples by ICP-AES and ICP-MS during boron neutron capture therapy.

PubMed

Linko, S; Revitzer, H; Zilliacus, R; Kortesniemi, M; Kouri, M; Savolainen, S

2008-01-01

The concept of boron neutron capture therapy (BNCT) involves infusion of a (10)B containing tracer into the patient's bloodstream followed by local neutron irradiation(s). Accurate estimation of the blood boron level for the treatment field before irradiation is required. Boron concentration can be quantified by inductively coupled plasma atomic emission spectrometry (ICP-AES), mass spectrometry (ICP-MS), spectrofluorometric and direct current atomic emission spectrometry (DCP-AES) or by prompt gamma photon detection methods. The blood boron concentrations were analysed and compared using ICP-AES and ICP-MS to ensure congruency of the results if the analysis had to be changed during the treatment, e.g. for technical reasons. The effect of wet-ashing on the results was studied in addition. The mean of all samples analysed with ICP-MS was 5.8 % lower than with ICP-AES coupled to wet-ashing (R (2) = 0.88). Without wet-ashing, the mean of all samples analysed with ICP-MS was 9.1 % higher than with ICP-AES (R (2) = 0.99). Boron concentration analysed from whole blood samples with ICP-AES correlated well with the values of ICP-MS with wet-ashing of the sample matrix, which is generally considered the reference method. When using these methods in parallel at certain intervals during the treatments, reliability of the blood boron concentration values remains satisfactory, taking into account the required accuracy of dose determination in the irradiation of cancer patients.

Metal ion transport quantified by ICP-MS in intact cells

PubMed Central

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

2016-01-01

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

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

PubMed

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

2016-02-03

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

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

Matrix and energy effects during in-situ determination of Cu isotope ratios by ultraviolet-femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Lazarov, Marina; Horn, Ingo

2015-09-01

Copper isotope compositions in Cu-bearing metals and minerals have been measured by deep (194 nm) ultraviolet femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry (UV-fsLA-MC-ICP-MS). Pure Cu-metal, brass, and several Cu-rich minerals (chalcopyrite, enargite, covellite, malachite and cuprite) have been investigated. A long-term reproducibility of better than 0.08‰ at the 95% confidence limit on the NIST SRM 976 (National Institute of Standards and Technology) Cu-metal standard has been achieved with this technique. The δ65Cu values for all samples have been calculated by standard-sample-standard bracketing with NIST SRM 976. All analyses have been carried out using Ni as a mass discrimination monitor added by nebulization prior to entering the plasma torch. For further verification samples have been analysed by conventional solution nebulization MC-ICP-MS and the results obtained have been compared with those from UV-fsLA-MC-ICP-MS. Several potential matrix-induced molecular interferences on the mineral copper isotope ratio, such as (32S33S)+ and (32S-16O17O)+ do not affect the Cu isotope measurements on sulfides, while hydrides, such as Zn-H or doubly-charged Sn2 + that interfere Ni isotopes can be either neglected or stripped by calculation. Matrix independent Cu-isotope measurements are sensitive to the energy density (fluence) applied onto the sample and can produce artificial shifts in the obtained δ65Cu values which are on the order of 3‰ for Cu-metal, 0.5‰ for brass and 0.3‰ for malachite when using energy density of up to 2 J/cm2 for ablation. A positive correlation between applied energy density and the magnitude of the isotope ratio shift has been found in the energy density range from 0.2 to 1.3 J/cm2 which is below the ablation threshold for ns-laser ablation. The results demonstrate that by using appropriate low fluence it is possible to measure Cu isotopic ratios in native copper and Cu-bearing sulfides, carbonates and oxides in situ with a precision of better than 0.1‰ (2SD) without using a matrix-matched standard during laser ablation analyses. Thus, this is a suitable tool to resolve Cu isotopic zoning larger than 0.1‰ in Cu-sulfides, carbonates and oxides.

Synthesis of amino-functionalized silica nanoparticles for preparation of new laboratory standards

NASA Astrophysics Data System (ADS)

Alvarez-Toral, Aitor; Fernández, Beatriz; Malherbe, Julien; Claverie, Fanny; Pecheyran, Christophe; Pereiro, Rosario

2017-12-01

Platinum group elements (PGEs) are particularly interesting analytes in different fields, including environmental samples as well as high cost materials that contain them, such as for example automotive catalysts. This type of solid samples could be analysed by laser ablation (LA) coupled to ICP-MS, which allow to significantly reducing the analysis time since the time-consuming processes for sample preparation are not required. There is a considerable demand of standards with high PGEs concentration for quantification purposes, which cannot be carried out easily using LA-ICP-MS because the available standards (i.e. NIST SRM 61 × series) do not have such analytes in the same concentration range. In this paper, a new strategy is proposed for the synthesis of homogeneous laboratory standards with Pt, Pd and Rh concentrations that range from 77 μg/g of Pd up to 2035 μg/g of Rh. The proposed strategy is based on the synthesis of monodisperse amino-functionalized amorphous silica nanoparticles, which can retain metal ions. In addition to Pt, Pd and Rh, three lanthanides were also added to the nanoparticles (La, Ce, Nd). Sturdy pressed pellets can be made from the resulting nanopowder without the use of any binder. Elemental composition of standards made of nanoparticles was analysed by conventional nebulization ICP-MS and their homogeneity was successfully evaluated by LA-ICP-MS.

Mass spectrometry of long-lived radionuclides

NASA Astrophysics Data System (ADS)

Becker, Johanna Sabine

2003-10-01

The capability of determining element concentrations at the trace and ultratrace level and isotope ratios is a main feature of inorganic mass spectrometry. The precise and accurate determination of isotope ratios of long-lived natural and artificial radionuclides is required, e.g. for their environmental monitoring and health control, for studying radionuclide migration, for age dating, for determining isotope ratios of radiogenic elements in the nuclear industry, for quality assurance and determination of the burn-up of fuel material in a nuclear power plant, for reprocessing plants, nuclear material accounting and radioactive waste control. Inorganic mass spectrometry, especially inductively coupled plasma mass spectrometry (ICP-MS) as the most important inorganic mass spectrometric technique today, possesses excellent sensitivity, precision and good accuracy for isotope ratio measurements and practically no restriction with respect to the ionization potential of the element investigated—therefore, thermal ionization mass spectrometry (TIMS), which has been used as the dominant analytical technique for precise isotope ratio measurements of long-lived radionuclides for many decades, is being replaced increasingly by ICP-MS. In the last few years instrumental progress in improving figures of merit for the determination of isotope ratio measurements of long-lived radionuclides in ICP-MS has been achieved by the application of a multiple ion collector device (MC-ICP-MS) and the introduction of the collision cell interface in order to dissociate disturbing argon-based molecular ions, to reduce the kinetic energy of ions and neutralize the disturbing noble gas ions (e.g. of 129Xe + for the determination of 129I). The review describes the state of the art and the progress of different inorganic mass spectrometric techniques such as ICP-MS, laser ablation ICP-MS vs. TIMS, glow discharge mass spectrometry, secondary ion mass spectrometry, resonance ionization mass spectrometry and accelerator mass spectrometry for the determination of long-lived radionuclides in quite different materials.

Evaluating intra- and inter- sample variability in Electron Spin Resonance dating of fossil teeth: an example from Cuesta de la Bajada site (Spain).

NASA Astrophysics Data System (ADS)

Duval, Mathieu; Grün, Rainer; Shao, Qingfeng; Martin, Loïc; Arnold, Lee J.

2017-04-01

Over the last decades, technological improvements have progressively enabled to significantly decrease the amount of material required for dating analyses. In particular, the combined use of laser ablation (LA) with ICP-MS opened new possibilities for high resolution in situ U-series analyses of fossil teeth. With this technique it is now possible to directly visualise the spatial distribution of U and Th isotopes in dental tissues. Moreover, the combination of LA-ICP-MS with Electron Spin Resonance (ESR) enables an increased sampling resolution, and offers the possibility to produce several ages for different areas within a given fossil tooth. To test the potential of this new approach, several fossil teeth were collected from the Middle Palaeolithic site of Cuesta de la Bajada (Teruel, Spain). Each tooth was divided into several subsamples, providing thus several combined US-ESR age results per tooth. For each subsample, ESR, high-resolution laser ablation and solution ICP-MS U-series analyses were systematically performed. Relative beta dose rate contributions from the different tissues and the sediment were also adjusted using DosiVox software and compared with those derived from the standard approach. The results of this work give some interesting insight into the intra- and inter- sample variability that may exist at a given site. The consistency of the final US-ESR age estimates obtained on teeth are also evaluated by comparison with the (semi)-independent results derived from ESR and Luminescence dating of optically bleached quartz grains collected from the same excavation area.

Comparison of analytical performances of inductively coupled plasma mass spectrometry and inductively coupled plasma atomic emission spectrometry for trace analysis of bismuth and bismuth oxide

NASA Astrophysics Data System (ADS)

Medvedev, Nickolay S.; Shaverina, Anastasiya V.; Tsygankova, Alphiya R.; Saprykin, Anatoly I.

2018-04-01

The paper presents а comparison of analytical performances of inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma atomic emission spectrometry (ICP-AES) for trace analysis of high purity bismuth and bismuth oxide. Matrix effects in the ICP-MS and ICP-AES methods were studied as a function of Bi concentration, ICP power and nebulizer flow rate. For ICP-MS the strong dependence of the matrix effects versus the atomic mass of analytes was observed. For ICP-AES the minimal matrix effects were achieved for spectral lines of analytes with low excitation potentials. The optimum degree of sample dilution providing minimum values of the limits of detection (LODs) was chosen. Both methods let us to reach LODs from n·10-7 to n·10-4 wt% for more than 50 trace elements. For most elements the LODs of ICP-MS were lower in comparison to ICP-AES. Validation of accuracy of the developed techniques was performed by "added-found" experiments and by comparison of the results of ICP-MS and ICP-AES analysis of high-purity bismuth oxide.

Preliminary characterisation of new glass reference materials (GSA-1G, GSC-1G, GSD-1G and GSE-1G) by laser ablation-inductively coupled plasma-mass spectrometry using 193 nm, 213 nm and 266 nm wavelengths

USGS Publications Warehouse

Guillong, M.; Hametner, K.; Reusser, E.; Wilson, S.A.; Gunther, D.

2005-01-01

New glass reference materials GSA-1G, GSC-1G, GSD-1G and GSE-1G have been characterised using a prototype solid state laser ablation system capable of producing wavelengths of 193 nm, 213 nm and 266 nm. This system allowed comparison of the effects of different laser wavelengths under nearly identical ablation and ICP operating conditions. The wavelengths 213 nm and 266 nm were also used at higher energy densities to evaluate the influence of energy density on quantitative analysis. In addition, the glass reference materials were analysed using commercially available 266 nm Nd:YAG and 193 nm ArF excimer lasers. Laser ablation analysis was carried out using both single spot and scanning mode ablation. Using laser ablation ICP-MS, concentrations of fifty-eight elements were determined with external calibration to the NIST SRM 610 glass reference material. Instead of applying the more common internal standardisation procedure, the total concentration of all element oxide concentrations was normalised to 100%. Major element concentrations were compared with those determined by electron microprobe. In addition to NIST SRM 610 for external calibration, USGS BCR-2G was used as a more closely matrix-matched reference material in order to compare the effect of matrix-matched and non matrix-matched calibration on quantitative analysis. The results show that the various laser wavelengths and energy densities applied produced similar results, with the exception of scanning mode ablation at 266 nm without matrix-matched calibration where deviations up to 60% from the average were found. However, results acquired using a scanning mode with a matrix-matched calibration agreed with results obtained by spot analysis. The increased abundance of large particles produced when using a scanning ablation mode with NIST SRM 610, is responsible for elemental fractionation effects caused by incomplete vaporisation of large particles in the ICP.

[Development of ICP-OES, ICP-MS and GF-AAS Methods for Simultaneous Quantification of Lead, Total Arsenic and Cadmium in Soft Drinks].

PubMed

Kataoka, Yohei; Watanabe, Takahiro; Hayashi, Tomoko; Teshima, Reiko; Matsuda, Rieko

2015-01-01

In this study, we developed methods to quantify lead, total arsenic and cadmium contained in various kinds of soft drinks, and we evaluated their performance. The samples were digested by common methods to prepare solutions for measurement by ICP-OES, ICP-MS and graphite furnace atomic absorption spectrometry (GF-AAS). After digestion, internal standard was added to the digestion solutions for measurements by ICP-OES and ICP-MS. For measurement by GF-AAS, additional purification of the digestion solution was conducted by back-extraction of the three metals into nitric acid solution after extraction into an organic solvent with ammonium pyrrolidine dithiocarbamate. Performance of the developed methods were evaluated for eight kinds of soft drinks.

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

PubMed

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

2013-01-01

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

An approach for quantification of platinum distribution in tissues by LA-ICP-MS imaging using isotope dilution analysis.

PubMed

Moraleja, I; Mena, M L; Lázaro, A; Neumann, B; Tejedor, A; Jakubowski, N; Gómez-Gómez, M M; Esteban-Fernández, D

2018-02-01

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been revealed as a convenient technique for trace elemental imaging in tissue sections, providing elemental 2D distribution at a quantitative level. For quantification purposes, in the last years several approaches have been proposed in the literature such as the use of CRMs or matrix matched standards. The use of Isotope Dilution (ID) for quantification by LA-ICP-MS has been also described, being mainly useful for bulk analysis but not feasible for spatial measurements so far. In this work, a quantification method based on ID analysis was developed by printing isotope-enriched inks onto kidney slices from rats treated with antitumoral Pt-based drugs using a commercial ink-jet device, in order to perform an elemental quantification in different areas from bio-images. For the ID experiments 194 Pt enriched platinum was used. The methodology was validated by deposition of natural Pt standard droplets with a known amount of Pt onto the surface of a control tissue, where could be quantified even 50pg of Pt, with recoveries higher than 90%. The amount of Pt present in the whole kidney slices was quantified for cisplatin, carboplatin and oxaliplatin-treated rats. The results obtained were in accordance with those previously reported. The amount of Pt distributed between the medullar and cortical areas was also quantified, observing different behavior for the three drugs. Copyright © 2017 Elsevier B.V. All rights reserved.

Determination of the structure and composition of Au-Ag bimetallic spherical nanoparticles using single particle ICP-MS measurements performed with normal and high temporal resolution.

PubMed

Kéri, Albert; Kálomista, Ildikó; Ungor, Ditta; Bélteki, Ádám; Csapó, Edit; Dékány, Imre; Prohaska, Thomas; Galbács, Gábor

2018-03-01

In this study, the information that can be obtained by combining normal and high resolution single particle ICP-MS (spICP-MS) measurements for spherical bimetallic nanoparticles (BNPs) was assessed. One commercial certified core-shell Au-Ag nanoparticle and three newly synthesized and fully characterized homogenous alloy Au-Ag nanoparticle batches of different composition were used in the experiments as BNP samples. By scrutinizing the high resolution spICP-MS signal time profiles, it was revealed that the width of the signal peak linearly correlates with the diameter of nanoparticles. It was also observed that the width of the peak for same-size nanoparticles is always significantly larger for Au than for Ag. It was also found that it can be reliably determined whether a BNP is of homogeneus alloy or core-shell structure and that, in the case of the latter, the core comprises of which element. We also assessed the performance of several ICP-MS based analytical methods in the analysis of the quantitative composition of bimetallic nanoparticles. Out of the three methods (normal resolution spICP-MS, direct NP nebulization with solution-mode ICP-MS, and solution-mode ICP-MS after the acid dissolution of the nanoparticles), the best accuracy and precision was achieved by spICP-MS. This method allows the determination of the composition with less than 10% relative inaccuracy and better than 3% precision. The analysis is fast and only requires the usual standard colloids for size calibration. Combining the results from both quantitative and structural analyses, the core diameter and shell thickness of core-shell particles can also be calculated. Copyright © 2017 Elsevier B.V. All rights reserved.

Analysis of rare earth elements in coal fly ash using laser ablation inductively coupled plasma mass spectrometry and scanning electron microscopy

NASA Astrophysics Data System (ADS)

Thompson, Robert L.; Bank, Tracy; Montross, Scott; Roth, Elliot; Howard, Bret; Verba, Circe; Granite, Evan

2018-05-01

Reference standard NIST SRM 1633b and FA 345, a fly ash sample from an eastern U.S. coal power plant, were analyzed to determine and quantify the mineralogical association of rare earth elements (REE). These analyses were completed using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and a scanning electron microscope, equipped with an energy-dispersive X-ray spectrometer (SEM-EDS). Internal standardization was avoided by quantifying elemental concentrations by normalizing to 100% oxides. Mineral grains containing elevated REE concentrations were found in diverse chemical environments, but were most commonly found in regions where Al and Si were predominant. Dividing the spot analyses into time segments yielded plots that showed the REE content changing over time as individual mineral grains were being ablated. SEM-EDS images of FA 345 confirmed the trends that were found in the LA-ICP-MS results. Small grains of apatite, monazite, or zircon were frequently observed as free mineral grains or embedded in amorphous aluminosilicate glass and were not associated with ferrous particles. This finding is consistent with previous reports that magnetic enrichment may be an effective way of concentrating non-magnetic REE phases. Furthermore, aggressive mechanical and chemical-based separation schemes will be required to separate and recover REE from aluminosilicate glass.

Single-cell analysis by ICP-MS/MS as a fast tool for cellular bioavailability studies of arsenite.

PubMed

Meyer, S; López-Serrano, A; Mitze, H; Jakubowski, N; Schwerdtle, T

2018-01-24

Single-cell inductively coupled plasma mass spectrometry (SC-ICP-MS) has become a powerful and fast tool to evaluate the elemental composition at a single-cell level. In this study, the cellular bioavailability of arsenite (incubation of 25 and 50 μM for 0-48 h) has been successfully assessed by SC-ICP-MS/MS for the first time directly after re-suspending the cells in water. This procedure avoids the normally arising cell membrane permeabilization caused by cell fixation methods (e.g. methanol fixation). The reliability and feasibility of this SC-ICP-MS/MS approach with a limit of detection of 0.35 fg per cell was validated by conventional bulk ICP-MS/MS analysis after cell digestion and parallel measurement of sulfur and phosphorus.

Experimental approaches to assessing the impact of a cesium chloride radiological dispersal device

USGS Publications Warehouse

Lee, S.; Gibb, Snyder E.; Barzyk, J.; McGee, J.; Koenig, A.

2008-01-01

The US EPA, as a part of the Chemical, Biological, Radiological-Nuclear, and Explosives (CBRNE) Research and Technology Initiative (CRTI) project team, is currently working to assess the impacts of an urban radiological dispersion device (RDD) and to develop containment and decontamination strategies. Three efforts in this area are currently underway: development of a laboratory-scale cesium chloride deposition method to mimic a RDD; assessment of cesium (Cs) penetration depth and pathways in urban materials using two dimensional (2-D) mapping laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS); and experimental determination of distribution coefficients (kd) for Cs in water-building material systems. It is critical that, when performing laboratory-scale experiments to assess the fate of Cs from an RDD, the Cs particle deposition method mimics the RDD deposition. Once Cs particles are deposited onto urban surfaces, 2-D mapping of Cs concentrations using LA-ICP-MS is a critical tool for determining Cs transport pathways through these materials. Lastly, distribution coefficients are critical for understanding the transport of Cs in urban settings when direct measurements of its penetration depth are unavailable. An assessment of the newly developed deposition method along with preliminary results from the penetration experiments are presented in this paper.

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

PubMed

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

2006-02-01

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

Isotope ratios of trace elements in samples from human nutrition studies determined by TIMS and ICP-MS: precision and accuracy compared.

PubMed

Turnlund, Judith R; Keyes, William R

2002-09-01

Stable isotopes are used with increasing frequency to trace the metabolic fate of minerals in human nutrition studies. The precision of the analytical methods used must be sufficient to permit reliable measurement of low enrichments and the accuracy should permit comparisons between studies. Two methods most frequently used today are thermal ionization mass spectrometry (TIMS) and inductively coupled plasma mass spectrometry (ICP-MS). This study was conducted to compare the two methods. Multiple natural samples of copper, zinc, molybdenum, and magnesium were analyzed by both methods to compare their internal and external precision. Samples with a range of isotopic enrichments that were collected from human studies or prepared from standards were analyzed to compare their accuracy. TIMS was more precise and accurate than ICP-MS. However, the cost, ease, and speed of analysis were better for ICP-MS. Therefore, for most purposes, ICP-MS is the method of choice, but when the highest degrees of precision and accuracy are required and when enrichments are very low, TIMS is the method of choice.

Characterization of Nanomaterials Using Field Flow Fractionation and Single Particle Inductively Coupled Plasma Mass Spectrometery (FFF-ICP-MS and SP-ICP-MS): Scientific Operating Procedure SOP-C

DTIC Science & Technology

2015-04-01

monodisperse particles. ENPs in environmental samples will likely have much broader size distributions and thus FFF-ICP-MS was tested over a greater...Figure 6). Resolution is based on ICP-MS sensitivity, and will likely decrease as the difference in particle diameter decreases. Second, this...Alvarez. 2006. Antibacterial activity of fullerene water suspensions: Effects of preparation method and particle size. Environmental Science

Inorganic trace analysis by mass spectrometry

NASA Astrophysics Data System (ADS)

Becker, Johanna Sabine; Dietze, Hans-Joachim

1998-10-01

Mass spectrometric methods for the trace analysis of inorganic materials with their ability to provide a very sensitive multielemental analysis have been established for the determination of trace and ultratrace elements in high-purity materials (metals, semiconductors and insulators), in different technical samples (e.g. alloys, pure chemicals, ceramics, thin films, ion-implanted semiconductors), in environmental samples (waters, soils, biological and medical materials) and geological samples. Whereas such techniques as spark source mass spectrometry (SSMS), laser ionization mass spectrometry (LIMS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), glow discharge mass spectrometry (GDMS), secondary ion mass spectrometry (SIMS) and inductively coupled plasma mass spectrometry (ICP-MS) have multielemental capability, other methods such as thermal ionization mass spectrometry (TIMS), accelerator mass spectrometry (AMS) and resonance ionization mass spectrometry (RIMS) have been used for sensitive mono- or oligoelemental ultratrace analysis (and precise determination of isotopic ratios) in solid samples. The limits of detection for chemical elements using these mass spectrometric techniques are in the low ng g -1 concentration range. The quantification of the analytical results of mass spectrometric methods is sometimes difficult due to a lack of matrix-fitted multielement standard reference materials (SRMs) for many solid samples. Therefore, owing to the simple quantification procedure of the aqueous solution, inductively coupled plasma mass spectrometry (ICP-MS) is being increasingly used for the characterization of solid samples after sample dissolution. ICP-MS is often combined with special sample introduction equipment (e.g. flow injection, hydride generation, high performance liquid chromatography (HPLC) or electrothermal vaporization) or an off-line matrix separation and enrichment of trace impurities (especially for characterization of high-purity materials and environmental samples) is used in order to improve the detection limits of trace elements. Furthermore, the determination of chemical elements in the trace and ultratrace concentration range is often difficult and can be disturbed through mass interferences of analyte ions by molecular ions at the same nominal mass. By applying double-focusing sector field mass spectrometry at the required mass resolution—by the mass spectrometric separation of molecular ions from the analyte ions—it is often possible to overcome these interference problems. Commercial instrumental equipment, the capability (detection limits, accuracy, precision) and the analytical application fields of mass spectrometric methods for the determination of trace and ultratrace elements and for surface analysis are discussed.

Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory - Determination of Elements in Whole-Water Digests Using Inductively Coupled Plasma-Optical Emission Spectrometry and Inductively Coupled Plasma-Mass Spectrometry

USGS Publications Warehouse

Garbarino, John R.; Struzeski, Tedmund M.

1998-01-01

Inductively coupled plasma-optical emission spectrometry (ICP-OES) and inductively coupled plasma-mass spectrometry (ICP-MS) can be used to determine 26 elements in whole-water digests. Both methods have distinct advantages and disadvantages--ICP-OES is capable of analyzing samples with higher elemental concentrations without dilution, however, ICP-MS is more sensitive and capable of determining much lower elemental concentrations. Both techniques gave accurate results for spike recoveries, digested standard reference-water samples, and whole-water digests. Average spike recoveries in whole-water digests were 100 plus/minus 10 percent, although recoveries for digests with high dissolved-solid concentrations were lower for selected elements by ICP-MS. Results for standard reference-water samples were generally within 1 standard deviation of hte most probable values. Statistical analysis of the results from 43 whole-water digest indicated that there was no significant difference among ICP-OES, ICP-MS, and former official methods of analysis for 24 of the 26 elements evaluated.

In situ location and U-Pb dating of small zircon grains in igneous rocks using laser ablation-inductively coupled plasma-quadrupole mass spectrometry

NASA Astrophysics Data System (ADS)

Sack, Patrick J.; Berry, Ron F.; Meffre, Sebastien; Falloon, Trevor J.; Gemmell, J. Bruce; Friedman, Richard M.

2011-05-01

A new U-Pb zircon dating protocol for small (10-50 μm) zircons has been developed using an automated searching method to locate zircon grains in a polished rock mount. The scanning electron microscope-energy-dispersive X ray spectrum-based automated searching method can routinely find in situ zircon grains larger than 5 μm across. A selection of these grains was ablated using a 10 μm laser spot and analyzed in an inductively coupled plasma-quadrupole mass spectrometer (ICP-QMS). The technique has lower precision (˜6% uncertainty at 95% confidence on individual spot analyses) than typical laser ablation ICP-MS (˜2%), secondary ion mass spectrometry (<1%), and isotope dilution-thermal ionization mass spectrometry (˜0.4%) methods. However, it is accurate and has been used successfully on fine-grained lithologies, including mafic rocks from island arcs, ocean basins, and ophiolites, which have traditionally been considered devoid of dateable zircons. This technique is particularly well suited for medium- to fine-grained mafic volcanic rocks where zircon separation is challenging and can also be used to date rocks where only small amounts of sample are available (clasts, xenoliths, dredge rocks). The most significant problem with dating small in situ zircon grains is Pb loss. In our study, many of the small zircons analyzed have high U contents, and the isotopic compositions of these grains are consistent with Pb loss resulting from internal α radiation damage. This problem is not significant in very young rocks and can be minimized in older rocks by avoiding high-U zircon grains.

ICP-MS: Analytical Method for Identification and Detection of Elemental Impurities.

PubMed

Mittal, Mohini; Kumar, Kapil; Anghore, Durgadas; Rawal, Ravindra K

2017-01-01

Aim of this article is to review and discuss the currently used quantitative analytical method ICP-MS, which is used for quality control of pharmaceutical products. ICP-MS technique has several applications such as determination of single elements, multi element analysis in synthetic drugs, heavy metals in environmental water, trace element content of selected fertilizers and dairy manures. ICP-MS is also used for determination of toxic and essential elements in different varieties of food samples and metal pollutant present in the environment. The pharmaceuticals may generate impurities at various stages of development, transportation and storage which make them risky to be administered. Thus, it is essential that these impurities must be detected and quantified. ICP-MS plays an important function in the recognition and revealing of elemental impurities. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Selenium speciation analysis of Misgurnus anguillicaudatus selenoprotein by HPLC-ICP-MS and HPLC-ESI-MS/MS

USDA-ARS?s Scientific Manuscript database

Analytical methods for selenium (Se) speciation were developed using high performance liquid chromatography (HPLC) coupled to either inductively coupled plasma mass spectrometry (ICP-MS) or electrospray ionization tandem mass spectrometry (ESI-MS/MS). Separations of selenomethionine (Se-Met) and sel...

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Analysis of metallic nanoparticles and their ionic counterparts in complex matrix by reversed-phase liquid chromatography coupled to ICP-MS.

PubMed

Yang, Yuan; Luo, Li; Li, Hai-Pu; Wang, Qiang; Yang, Zhao-Guang; Qu, Zhi-Peng; Ding, Ru

2018-05-15

Developing quantification and characterization methodology for metallic nanoparticles (MNPs) and their ionic component in complex matrix are crucial for the evaluation of their environmental behavior and health risks to humans. In this study, reversed phase high performance liquid chromatography combined ICP-MS was established for the characterization of MNPs in complex matrix. The ionic component could be separated from NPs with the optimized parameters of aqueous mobile phase. Good linear relationship between average diameter and retention time of NPs was obtained using HPLC-ICP-MS and the size smaller than 40 nm could be determined with this method, the detected results were in accordance with TEM results. The low detection limit of AuNPs and Au(Ⅲ) (both in sub-μg/L level) showed that this method was promising for the characterization of AuNPs and Au(Ⅲ) in environmental water. The mass concentration of ionic Au(Ⅲ) in environmental water could be detected using the proposed HPLC-ICP-MS and the concentration of AuNPs was obtained by subtracting the Au(Ⅲ) concentration from the total Au (The concentration of total Au was detected by ICP-MS after microwave digestion). Furthermore this proposed HPLC-ICP-MS method and single particle-ICPMS (SP-ICP-MS) was used for the analysis of the Ag speciation in commercial antibacterial products. Copyright © 2018 Elsevier B.V. All rights reserved.

A comparison of sample preparation strategies for biological tissues and subsequent trace element analysis using LA-ICP-MS.

PubMed

Bonta, Maximilian; Török, Szilvia; Hegedus, Balazs; Döme, Balazs; Limbeck, Andreas

2017-03-01

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is one of the most commonly applied methods for lateral trace element distribution analysis in medical studies. Many improvements of the technique regarding quantification and achievable lateral resolution have been achieved in the last years. Nevertheless, sample preparation is also of major importance and the optimal sample preparation strategy still has not been defined. While conventional histology knows a number of sample pre-treatment strategies, little is known about the effect of these approaches on the lateral distributions of elements and/or their quantities in tissues. The technique of formalin fixation and paraffin embedding (FFPE) has emerged as the gold standard in tissue preparation. However, the potential use for elemental distribution studies is questionable due to a large number of sample preparation steps. In this work, LA-ICP-MS was used to examine the applicability of the FFPE sample preparation approach for elemental distribution studies. Qualitative elemental distributions as well as quantitative concentrations in cryo-cut tissues as well as FFPE samples were compared. Results showed that some metals (especially Na and K) are severely affected by the FFPE process, whereas others (e.g., Mn, Ni) are less influenced. Based on these results, a general recommendation can be given: FFPE samples are completely unsuitable for the analysis of alkaline metals. When analyzing transition metals, FFPE samples can give comparable results to snap-frozen tissues. Graphical abstract Sample preparation strategies for biological tissues are compared with regard to the elemental distributions and average trace element concentrations.

Evaluation of Nonferrous Metals as Potential In Vivo Tracers of Transferrin-Based Therapeutics

NASA Astrophysics Data System (ADS)

Zhao, Hanwei; Wang, Shunhai; Nguyen, Son N.; Elci, S. Gokhan; Kaltashov, Igor A.

2016-02-01

Transferrin (Tf) is a promising candidate for targeted drug delivery. While development of such products is impossible without the ability to monitor biodistribution of Tf-drug conjugates in tissues and reliable measurements of their levels in blood and other biological fluids, the presence of very abundant endogenous Tf presents a significant impediment to such efforts. Several noncognate metals have been evaluated in this work as possible tracers of exogenous transferrin in complex biological matrices using inductively coupled plasma mass spectrometry (ICP MS) as a detection tool. Placing Ni(II) on a His-tag of recombinant Tf resulted in formation of a marginally stable protein-metal complex, which readily transfers the metal to ubiquitous physiological scavengers, such as serum albumin. An alternative strategy targeted iron-binding pockets of Tf, where cognate Fe(III) was replaced by metal ions known to bind this protein. Both Ga(III) and In(III) were evaluated, with the latter being vastly superior as a tracer (stronger binding to Tf unaffected by the presence of metal scavengers and the retained ability to associate with Tf receptor). Spiking serum with indium-loaded Tf followed by ICP MS detection demonstrated that protein quantities as low as 0.04 nM can be readily detected in animal blood. Combining laser ablation with ICP MS detection allows distribution of exogenous Tf to be mapped within animal tissue cross-sections with spatial resolution exceeding 100 μm. The method can be readily extended to a range of other therapeutics where metalloproteins are used as either carriers or payloads.

Mapping trace element distribution in fossil teeth and bone with LA-ICP-MS

NASA Astrophysics Data System (ADS)

Hinz, E. A.; Kohn, M. J.

2009-12-01

Trace element profiles were measured in fossil bones and teeth from the late Pleistocene (c. 25 ka) Merrell locality, Montana, USA, by using laser-ablation ICP-MS. Laser-ablation ICP-MS can collect element counts along predefined tracks on a sample’s surface using a constant ablation speed allowing for rapid spatial sampling of element distribution. Key elements analyzed included common divalent cations (e.g. Sr, Zn, Ba), a suite of REE (La, Ce, Nd, Sm, Eu, Yb), and U, in addition to Ca for composition normalization and standardization. In teeth, characteristic diffusion penetration distances for all trace elements are at least a factor of 4 greater in traverses parallel to the dentine-enamel interface (parallel to the growth axis of the tooth) than perpendicular to the interface. Multiple parallel traverses in sections parallel and perpendicular to the tooth growth axis were transformed into trace element maps, and illustrate greater uptake of all trace elements along the central axis of dentine compared to areas closer to enamel, or within the enamel itself. Traverses in bone extending from the external surface, through the thickness of cortical bone and several mm into trabecular bone show major differences in trace element uptake compared to teeth: U and Sr are homogeneous, whereas all REE show a kinked profile with high concentrations on outer surfaces that decrease by several orders of magnitude within a few mm inward. The Eu anomaly increases uniformly from the outer edge of bone inward, whereas the Ce anomaly decreases slightly. These observations point to major structural anisotropies in trace element transport and uptake during fossilization, yet transport and uptake of U and REE are not resolvably different. In contrast, transport and uptake of U in bone must proceed orders of magnitude faster than REE as U is homogeneous whereas REE exhibit strong gradients. The kinked REE profiles in bone unequivocally indicate differential transport rates, consistent with a double-medium diffusion model in which microdomains with slow diffusivities are bounded by fast-diffusing pathways.

Characterisation of a natural quartz crystal as a reference material for microanalytical determination of Ti, Al, Li, Fe, Mn, Ga and Ge

USGS Publications Warehouse

Audetat, Andreas; Garbe-Schonberg, Dieter; Kronz, Andreas; Pettke, Thomas; Rusk, Brian G.; Donovan, John J.; Lowers, Heather

2015-01-01

A natural smoky quartz crystal from Shandong province, China, was characterised by laser ablation ICP-MS, electron probe microanalysis (EPMA) and solution ICP-MS to determine the concentration of twenty-four trace and ultra trace elements. Our main focus was on Ti quantification because of the increased use of this element for titanium-in-quartz (TitaniQ) thermobarometry. Pieces of a uniform growth zone of 9 mm thickness within the quartz crystal were analysed in four different LA-ICP-MS laboratories, three EPMA laboratories and one solution-ICP-MS laboratory. The results reveal reproducible concentrations of Ti (57 ± 4 μg g-1), Al (154 ± 15 μg g-1), Li (30 ± 2 μg g-1), Fe (2.2 ± 0.3 μg g-1), Mn (0.34 ± 0.04 μg g-1), Ge (1.7 ± 0.2 μg g-1) and Ga (0.020 ± 0.002 μg g-1) and detectable, but less reproducible, concentrations of Be, B, Na, Cu, Zr, Sn and Pb. Concentrations of K, Ca, Sr, Mo, Ag, Sb, Ba and Au were below the limits of detection of all three techniques. The uncertainties on the average concentration determinations by multiple techniques and laboratories for Ti, Al, Li, Fe, Mn, Ga and Ge are low; hence, this quartz can serve as a reference material or a secondary reference material for microanalytical applications involving the quantification of trace elements in quartz.

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

NASA Technical Reports Server (NTRS)

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

2017-01-01

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

Applications of inductively coupled plasma-mass spectrometry in environmental radiochemistry

USGS Publications Warehouse

Grain, J.S.

1996-01-01

The state of the art in ICP-MS is now such that there are few discernible differences between radiochemical and mass spectrometric determinations of longlived radionuclides. Indeed, ICP-MS may provide better (more sensitive) data for many radionuclides, depending upon how one wishes to define "long-lived." In lowlevel determinations, sample preparation remains an important part of the analytical procedure, even with ICP-MS, but the speed and isotopic selectivity of the mass spectrometer appear to offer distinct procedural advantages over radiochemical techniques. Therefore, "radioanalytical" ICP-MS applications should continue to grow, especially in the area of radiation protection, but further research (on efficient sample introduction, for example) and method development may be required to get ICP-MS "off the ground" in the geochemical research areas that have traditionally been supported by radiochemistry.

Introduction of organic/hydro-organic matrices in inductively coupled plasma optical emission spectrometry and mass spectrometry: a tutorial review. Part II. Practical considerations.

PubMed

Leclercq, Amélie; Nonell, Anthony; Todolí Torró, José Luis; Bresson, Carole; Vio, Laurent; Vercouter, Thomas; Chartier, Frédéric

2015-07-23

Inductively coupled plasma optical emission spectrometry (ICP-OES) and mass spectrometry (ICP-MS) are increasingly used to carry out analyses in organic/hydro-organic matrices. The introduction of such matrices into ICP sources is particularly challenging and can be the cause of numerous drawbacks. This tutorial review, divided in two parts, explores the rich literature related to the introduction of organic/hydro-organic matrices in ICP sources. Part I provided theoretical considerations associated with the physico-chemical properties of such matrices, in an attempt to understand the induced phenomena. Part II of this tutorial review is dedicated to more practical considerations on instrumentation, instrumental and operating parameters, as well as analytical strategies for elemental quantification in such matrices. Two important issues are addressed in this part: the first concerns the instrumentation and optimization of instrumental and operating parameters, pointing out (i) the description, benefits and drawbacks of different kinds of nebulization and desolvation devices and the impact of more specific instrumental parameters such as the injector characteristics and the material used for the cone; and, (ii) the optimization of operating parameters, for both ICP-OES and ICP-MS. Even if it is at the margin of this tutorial review, Electrothermal Vaporization and Laser Ablation will also be shortly described. The second issue is devoted to the analytical strategies for elemental quantification in such matrices, with particular insight into the isotope dilution technique, particularly used in speciation analysis by ICP-coupled separation techniques. Copyright © 2015 Elsevier B.V. All rights reserved.

Diffusivities of Redox-Sensitive Elements in Basalt vs. Oxygen Fugacity Determined by LA-ICP-MS

NASA Technical Reports Server (NTRS)

Szumila, Ian; Danielson, Lisa; Trail, Dustin

2017-01-01

Several diffusion experiments were conducted in a piston cylinder device across a range of oxygen fugacities (FMQ-3 FMQ-1.2, FMQ+6) at 1 GPa and 1300 C. This was done to explore the effects of oxygen fugacity (fO2) on diffusivity of redox sensitive trace elements. This allows investigation of how these elements diffuse across the fO2 range encountered in different reservoirs on planets and moons in our solar system. The University of Rochester LA-ICP-MS system was used for analysis of samples. Analyses were conducted using an Agilent 7900 quadrupole mass spectrometer connected to a Photon Machines 193 nm G2 laser ablation (LA) system equipped with a HelEx 2-volume sample chamber. Spots used were 35 micrometers circles spaced at 65 micrometers intervals. Laser fluence was 7.81 J/cm^2 with a rep rate of 10 Hz. The iolite software package was used to reduce data collected from laser ablation analysis of experiments with Si-29 used as the internal standard isotope. Iolite's global fit module was used to simultaneously fit elements' diffusivities in each experiment while keeping the Matano interface constant. Elements analysed include V, Nb, W, Mo, La, Ce, Pr, Sm, Eu, Gd, Ta, and W. Figures

Validation and use of three complementary analytical methods (LC-FLS, LC-MS/MS and ICP-MS) to evaluate the pharmacokinetics, biodistribution and stability of motexafin gadolinium in plasma and tissues.

PubMed

Miles, Dale R; Mesfin, Mimi; Mody, Tarak D; Stiles, Mark; Lee, Jean; Fiene, John; Denis, Bernie; Boswell, Garry W

2006-05-01

Liquid chromatography-fluorescence (LC-FLS), liquid chromatography-tandem mass spectrometry (LC-MS/MS) and inductively coupled plasma-mass spectrometry (ICP-MS) methods were developed and validated for the evaluation of motexafin gadolinium (MGd, Xcytrin) pharmacokinetics and biodistribution in plasma and tissues. The LC-FLS method exhibited the greatest sensitivity (0.0057 microg mL(-1)), and was used for pharmacokinetic, biodistribution, and protein binding studies with small sample sizes or low MGd concentrations. The LC-MS/MS method, which exhibited a short run time and excellent selectivity, was used for routine clinical plasma sample analysis. The ICP-MS method, which measured total Gd, was used in conjunction with LC methods to assess MGd stability in plasma. All three methods were validated using human plasma. The LC-FLS method was also validated using plasma, liver and kidneys from mice and rats. All three methods were shown to be accurate, precise and robust for each matrix validated. For three mice, the mean (standard deviation) concentration of MGd in plasma/tissues taken 5 hr after dosing with 23 mg kg(-1) MGd was determined by LC-FLS as follows: plasma (0.025+/-0.002 microg mL(-1)), liver (2.89+/-0.45 microg g(-1)), and kidney (6.09+/-1.05 microg g(-1)). Plasma samples from a subset of patients with brain metastases from extracranial tumors were analyzed using both LC-MS/MS and ICP-MS methods. For a representative patient, > or = 90% of the total Gd in plasma was accounted for as MGd over the first hour post dosing. By 24 hr post dosing, 63% of total Gd was accounted for as MGd, indicating some metabolism of MGd.

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

NASA Astrophysics Data System (ADS)

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

2010-05-01

This work focuses on an innovative methodological approach to investigate in situ chemical composition of trace and rare earth (REE) elements in discrete soil features from different soil horizons: laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was applied to clay coatings, pedogenic matrix and skeletal parent rock fragments in thin sections, coupled with traditional pedological investigations, specially clay mineralogy and micromorphology. Analyses were performed on 80 μm-thick sections obtained from undisturbed soil samples, which represent three reddish argillic (Bt) horizons from an Alfisol developed on late Pleistocene slope deposits and three brown organic-mineral (A) horizons from an Entisol formed on Holocene aggrading fluvial sediments in the Muravera area (southeast Sardinia, Italy). Validation of the LA-ICP-MS technique provides in situ accurate and reproducible (RSD 13-18%) analysis of low concentration trace elements in the studied soil samples (0.001-0.1 ppm). Our results showed a high reliability of this method on soil thin sections and revealed that concentrations of trace and rare earth elements in the different portions of a soil profile can be used to investigate their distribution, as a response to soil-forming processes. A general trend of increase of most trace elements from rock fragments to (both clayey and organic-rich) soil matrix, to clay coatings in argillic horizons is clearly highlighted. On this basis a prominent role of pedogenetic processes in element fractionation and distribution during weathering can be supposed. In particular, element adsorption onto reactive sites of organic matter and clay particles (and possibly Fe-oxyhydroxides) and clay illuviation appear the main pedogenetic processes able to promote element enrichment after their release from the weathering of primary minerals. As clay coatings exhibit the highest concentration of trace elements, and specifically of REEs, and represent the most mobile solid phase in the soil profile, this tool can be used as a reliable indicator of soil weathering after a preliminary assessment of illuvial clay pedofeatures. This feature is consistent with a progressively increasing time of soil development, testified by the older age of the Alfisol than the Entisol profile. Such a result is also supported by a comparison of trace element concentrations between the clay and the fine earth fractions of the bulk soil horizons performed with ICP-MS in solution, showing REE enrichment in the clays from the former soil. Moreover, trace element patterns show some discontinuous trends among soil features of different horizons, coherently with erosive and/or depositional discontinuities described in the field.

A new method for stable lead isotope extraction from seawater.

PubMed

Zurbrick, Cheryl M; Gallon, Céline; Flegal, A Russell

2013-10-24

A new technique for stable lead (Pb) isotope extraction from seawater is established using Toyopearl AF-Chelate 650M(®) resin (Tosoh Bioscience LLC). This new method is advantageous because it is semi-automated and relatively fast; in addition it introduces a relatively low blank by minimizing the volume of chemicals used in the extraction. Subsequent analyses by HR ICP-MS have a good relative external precision (2σ) of 3.5‰ for (206)Pb/(207)Pb, while analyses by MC-ICP-MS have a better relative external precision of 0.6‰. However, Pb sample concentrations limit MC-ICP-MS analyses to (206)Pb, (207)Pb, and (208)Pb. The method was validated by processing the common Pb isotope reference material NIST SRM-981 and several GEOTRACES intercalibration samples, followed by analyses by HR ICP-MS, all of which showed good agreement with previously reported values. Copyright © 2013 Elsevier B.V. All rights reserved.

Right Ventricular Pacing for Assessment of Cavo-Tricuspid Isthmus Block.

PubMed

Venkataraman, Ganesh; Wish, Marc; Friehling, Ted; Strickberger, S Adam

2016-01-01

Background: Cavo-tricuspid isthmus (CTI) dependent atrial flutter is typically treated with cardiac ablation. Standard techniques to assess CTI block after ablation can be technically challenging. Right ventricular (RV) pacing may allow for another technique to assess CTI block after ablation. Objective: The purpose of this study was to evaluate RV pacing as a method to assess CTI block after ablation of CTI dependent atrial flutter, and define endpoints of ablation using this technique. Methods: 28 patients undergoing ablation of CTI dependent atrial flutter with intact ventriculoatrial (VA) conduction were prospectively enrolled in this study and underwent the RV pacing protocol, as well as standard coronary sinus (CS) pacing techniques to assess CTI block. Results: The mean trans-isthmus conduction interval during CS pacing (TICI CS ) at 600 and 400ms after CTI ablation was 168 +/- 9ms and 175 +/- 18ms, respectively. The mean trans-isthmus conduction interval during RV pacing (TICI RV ) at 600ms and 400ms after CTI ablation was 109 +/- 5ms and 111 +/- 5ms, respectively. A TICI RV >100ms was associated with a successful outcome after CTI ablation. Conclusions: RV pacing may add incremental value in the assessment of CTI block in patients undergoing ablation of CTI dependent atrial flutter.

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

PubMed

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

2016-06-01

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

Spatial investigation of the elemental distribution in Wilson's disease liver after d-penicillamine treatment by LA-ICP-MS.

PubMed

Hachmöller, Oliver; Zibert, Andree; Zischka, Hans; Sperling, Michael; Groba, Sara Reinartz; Grünewald, Inga; Wardelmann, Eva; Schmidt, Hartmut H-J; Karst, Uwe

2017-12-01

At present, the copper chelator d-penicillamine (DPA) is the first-line therapy of Wilson's disease (WD), which is characterized by an excessive copper overload. Lifelong DPA treatments aim to reduce the amount of detrimental excess copper retention in the liver and other organs. Although DPA shows beneficial effect in many patients, it may cause severe adverse effects. Despite several years of copper chelation therapy, discontinuation of DPA therapy can be linked to a rapidly progressing liver failure, indicating a high residual liver copper load. In order to investigate the spatial distribution of remaining copper and additional elements, such as zinc and iron, in rat and human liver samples after DPA treatment, a high resolution (spotsize of 10μm) laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) imaging method was applied. Untreated LPP -/- rats, an established animal model for WD, appeared with a high overall copper concentration and a copper distribution of hotspots distributed over the liver tissue. In contrast, a low (>2-fold decreased) overall copper concentration was detected in liver of DPA treated animals. Importantly, however, copper distribution was highly inhomogeneous with lowest concentrations in direct proximity to blood vessels, as observed using novel zonal analysis. A human liver needle biopsy of a DPA treated WD patient substantiated the finding of an inhomogeneous copper deposition upon chelation therapy. In contrast, comparatively homogenous distributions of zinc and iron were observed. Our study indicates that a high resolution LA-ICP-MS analysis of liver samples is excellently suited to follow efficacy of chelator therapy in WD patients. Copyright © 2017 Elsevier GmbH. All rights reserved.

Results of LA-ICP-MS sulfide mapping from Algoma-type BIF gold systems with implications for the nature of mineralizing fluids, metal sources, and deposit models

NASA Astrophysics Data System (ADS)

Gourcerol, B.; Kontak, D. J.; Thurston, P. C.; Petrus, J. A.

2018-01-01

Quantitative laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) element distribution maps combined with traverse mode analyses have been acquired on various sulfides (pyrite, pyrrhotite, arsenopyrite) from three Canadian Algoma-type BIF-hosted gold deposits ( 4 Moz Au Meadowbank, ≥ 2.8 Moz Au Meliadine district, 6 Moz Au Musselwhite). These data, in conjunction with detailed petrographic and SEM-EDS observations, provide insight into the nature and relative timing of gold events, the presence and implication of trace element zoning regarding crystallization processes, and elemental associations that fingerprint gold events. Furthermore, the use of an innovative method of processing the LA-ICP-MS data in map and traverse modes, whereby the results are fragmented into time-slice data, to generate various binary plots (Ag versus Ni) provides a means to identify elemental associations (Te, Bi) not otherwise apparent. This integrated means of treating geochemical data, along with petrography, allows multiple gold events and remobilization processes to be recognized and their elemental associations determined. The main gold event in each of these deposits is characterized by the coupling of an As-Se-Te-Ag element association coincident with intense stratabound sulfide-replacement of the Fe-rich host rock. Additionally, the data indicate presence of a later remobilization event, which upgraded the Au tenor, as either non-refractory or refractory type, along fracture networks due to the ingress of subsequent base metal-bearing metamorphic fluids (mainly a Pb-Bi association). Furthermore, the data reveal a stratigraphic influence, as reflected in the elemental associations and the elemental enrichments observed and the nature of the sulfide phase hosting the gold mineralization (arsenopyrite versus pyrite).

Direct solid analysis of powdered tungsten carbide hardmetal precursors by laser-induced argon spark ablation with inductively coupled plasma atomic emission spectrometry.

PubMed

Holá, Markéta; Kanický, Viktor; Mermet, Jean-Michel; Otruba, Vítezslav

2003-12-01

The potential of the laser-induced argon spark atomizer (LINA-Spark atomizer) coupled with ICP-AES as a convenient device for direct analysis of WC/Co powdered precursors of sintered hardmetals was studied. The samples were presented for the ablation as pressed pellets prepared by mixing with powdered silver binder containing GeO2 as internal standard. The pellets were ablated with the aid of a Q-switched Nd:YAG laser (1064 nm) focused 16 mm behind the target surface with a resulting estimated power density of 5 GW cm(-2). Laser ablation ICP-AES signals were studied as a function of ablation time, and the duration of time prior to measurement (pre-ablation time) which was necessary to obtain reliable results was about 40 s. Linear calibration plots were obtained up to 10% (m/m) Ti, 9% Ta and 3.5% Nb both without internal standardization and by using germanium as an added internal standard or tungsten as a contained internal standard. The relative uncertainty at the centroid of the calibration line was in the range from +/- 6% to +/- 11% for Nb, Ta and Ti both with and without internal standardisation by Ge. A higher spread of points about the regression was observed for cobalt for which the relative uncertainty at the centroid was in the range from +/- 9% to +/- 14%. Repeatability of results was improved by the use of both Ge and W internal standards. The lowest determinable quantities calculated for calibration plots were 0.060% Co, 0.010% Nb, 0.16% Ta and 0.030% Ti with internal standardization by Ge. The LA-ICP-AES analyses of real samples led to good agreement with the results obtained by solution-based ICP determination with a relative bias not exceeding 10%. The elimination of the dissolution procedure of powdered tungsten (Nb, Ta, Ti) carbide is the principal advantage of the developed LA-ICP-AES method.

Chromatographic-ICPMS methods for trace element and isotope analysis of water and biogenic calcite

NASA Astrophysics Data System (ADS)

Klinkhammer, G. P.; Haley, B. A.; McManus, J.; Palmer, M. R.

2003-04-01

ICP-MS is a powerful technique because of its sensitivity and speed of analysis. This is especially true for refractory elements that are notoriously difficult using TIMS and less energetic techniques. However, as ICP-MS instruments become more sensitive to elements of interest they also become more sensitive to interference. This becomes a pressing issue when analyzing samples with high total dissolved solids. This paper describes two trace element methods that overcome these problems by using chromatographic techniques to precondition samples prior to analysis by ICP-MS: separation of rare earth elements (REEs) from seawater using HPLC-ICPMS, and flow-through dissolution of foraminiferal calcite. Using HPLC in combination with ICP-MS it is possible to isolate the REEs from matrix, other transition elements, and each other. This method has been developed for small volume samples (5ml) making it possible to analyze sediment pore waters. As another example, subjecting foram shells to flow-through reagent addition followed by time-resolved analysis in the ICP-MS allows for systematic cleaning and dissolution of foram shells. This method provides information about the relationship between dissolution tendency and elemental composition. Flow-through is also amenable to automation thus yielding the high sample throughput required for paleoceanography, and produces a highly resolved elemental matrix that can be statistically analyzed.

Comparative evaluation of GFAAS and ICP-MS for analyses of cadmium in blood.

PubMed

Fukui, Yoshinari; Ohashi, Fumiko; Sakuragi, Sonoko; Moriguchi, Jiro; Ikeda, Masayuki

2011-01-01

Cadmium in blood (Cd-B) is an important indicator, next to Cd in urine, in biological monitoring of exposure to Cd. The present study was initiated to examine compatibility in results of analysis for Cd-B between graphite furnace atomic absorption spectrophotometry (GFAAS) and inductively-coupled plasma mass-spectrometry (ICP-MS). For this purpose, 1,159 blood samples were collected from adult women (with no occupational exposure to Cd) in eight prefectures nation-widely in Japan. The samples were analyzed by the two methods; geometric mean (the maximum) concentrations were 1.22 (6.90) μg/l by ICP-MS, and 1.47 (7.40) μg/l by GFAAS. Statistical analyses showed that there was a close correlation between the results by the two methods. The regression line (with ICP-MS and GFAAS results as an independent variable and a dependent variable, respectively) had a slope close to one and an intercept next to zero to suggest that ICP-MS gave values compatible with that of GFAAS. Further analysis with the ratio of Cd-B by GFAAS over that by ICP-MS revealed that the two results were close to each other, and that the agreement was even closer when Cd-B was >2 μg/l. Thus, the two methods can be employed inter-convertibly when Cd-B is relatively high, e.g. >2 μg/l. Care may need to be practiced, however, for possible 'between methods' difference when Cd-B is low, e.g., ≤2 μg/l.

Corrosion Protection Mechanisms of Rare-Earth Compounds Based on Cerium and Praseodymium

DTIC Science & Technology

2012-04-01

Annular Dark Field IMC–Intermetallic compound LA-ICP-MS Laser Ablation Inductively Coupled Plasma Mass Spectrometry MPY—Mils per year (a measure of...currently researching CeCCs. ................................. 20   Table 2.   Mass percent losses during various ranges of thermal treatment for Pr6O11...analysis data of corrosion product in an 084 primer series scribe following 500 hours of salt spray exposure as detected by mass spectrometry

Solution-based calibration strategy for laser ablation-inductively coupled plasma-mass spectrometry using desolvating nebulizer system

NASA Astrophysics Data System (ADS)

Zhang, Guoxia; Li, Qing; Zhu, Yan; Wang, Zheng

2018-07-01

An additional quantification strategy using a desolvating nebulizer system (DNS) for solution-based calibration was developed. For quantitative analysis, laser ablation (LA) and DNS-generated aerosols were coupled using a "Y" connector and introduced into the inductively coupled plasma (ICP). These aerosols were also observed by scanning electron microscopy following collection on a silicon chip. Internal standards (108Ag, 64Cu, 89Y) were used to correct for the different aerosol transport efficiencies between the DNS and LA. The correlation coefficients of the calibration curves for all elements ranged from 0.9986 to 0.9999. Standard reference materials (NIST 610-616 and GBW08407-08411) were used to demonstrate the accuracy and precision of the method. The results were in good agreement with certified values, and the relative standard deviation (RSD) of most elements was <3%. The limits of detection (LODs) for 50Cr, 55Mn, 59Co, 60Ni, 66Zn, 89Y, 110Cd, 139La, 140Ce, 146Nd, 147Sm, 157Gd, 163Dy, 166Er, and 208Pb were 23, 3, 3, 19, 31, 4, 12, 0.4, 0.9, 0.1, 0.2, 2, 0.3, 0.4, and 21 ng/g, respectively, which were significantly better than those obtained by other methods. Further, this approach was applied for the analysis of multiple elements in biological tissues, and the results were in good agreement with those obtained using solution-based inductively coupled plasma-mass spectrometry (ICP-MS).

The potential of using laser ablation inductively coupled plasma time of flight mass spectrometry (LA-ICP-TOF-MS) in the forensic analysis of micro debris.

PubMed

Scadding, Cameron J; Watling, R John; Thomas, Allen G

2005-08-15

The majority of crimes result in the generation of some form of physical evidence, which is available for collection by crime scene investigators or police. However, this debris is often limited in amount as modern criminals become more aware of its potential value to forensic scientists. The requirement to obtain robust evidence from increasingly smaller sized samples has required refinement and modification of old analytical techniques and the development of new ones. This paper describes a new method for the analysis of oxy-acetylene debris, left behind at a crime scene, and the establishment of its co-provenance with single particles of equivalent debris found on the clothing of persons of interest (POI). The ability to rapidly determine and match the elemental distribution patterns of debris collected from crime scenes to those recovered from persons of interest is essential in ensuring successful prosecution. Traditionally, relatively large amounts of sample (up to several milligrams) have been required to obtain a reliable elemental fingerprint of this type of material [R.J. Walting , B.F. Lynch, D. Herring, J. Anal. At. Spectrom. 12 (1997) 195]. However, this quantity of material is unlikely to be recovered from a POI. This paper describes the development and application of laser ablation inductively coupled plasma time of flight mass spectrometry (LA-ICP-TOF-MS), as an analytical protocol, which can be applied more appropriately to the analysis of micro-debris than conventional quadrupole based mass spectrometry. The resulting data, for debris as small as 70mum in diameter, was unambiguously matched between a single spherule recovered from a POI and a spherule recovered from the scene of crime, in an analytical procedure taking less than 5min.

Novel Bioimaging Techniques of Metals by Laser Ablation Inductively Coupled Plasma Mass Spectrometry for Diagnosis Of Fibrotic and Cirrhotic Liver Disorders

PubMed Central

Gassler, Nikolaus; Bosserhoff, Anja K.; Becker, J. Sabine

2013-01-01

Background and Aims Hereditary disorders associated with metal overload or unwanted toxic accumulation of heavy metals can lead to morbidity and mortality. Patients with hereditary hemochromatosis or Wilson disease for example may develop severe hepatic pathology including fibrosis, cirrhosis or hepatocellular carcinoma. While relevant disease genes are identified and genetic testing is applicable, liver biopsy in combination with metal detecting techniques such as energy-dispersive X-ray spectroscopy (EDX) is still applied for accurate diagnosis of metals. Vice versa, several metals are needed in trace amounts for carrying out vital functions and their deficiency due to rapid growth, pregnancy, excessive blood loss, and insufficient nutritional or digestive uptake results in organic and systemic shortcomings. Established in situ techniques, such as EDX-ray spectroscopy, are not sensitive enough to analyze trace metal distribution and the quantification of metal images is difficult. Methods In this study, we developed a quantitative biometal imaging technique of human liver tissue by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) in order to compare the distribution of selected metals in cryo-sections of healthy and fibrotic/cirrhotic livers. Results Most of the metals are homogeneous distributed within the normal tissue, while they are redirected within fibrotic livers resulting in significant metal deposits. Moreover, total iron and copper concentrations in diseased liver were found about 3-5 times higher than in normal liver samples. Conclusions Biometal imaging via LA-ICP-MS is a sensitive innovative diagnostic tool that will impact clinical practice in identification and evaluation of hepatic metal disorders and to detect subtle metal variations during ongoing hepatic fibrogenesis. PMID:23505552

Hair as a Biomarker of Environmental Manganese Exposure

PubMed Central

Eastman, Rachel R.; Jursa, Tom P.; Benedetti, Chiara; Lucchini, Roberto G.; Smith, Donald R.

2013-01-01

The absence of well-validated biomarkers of manganese (Mn) exposure in children remains a major obstacle for studies of Mn toxicity. We developed a hair cleaning methodology to establish the utility of hair as an exposure biomarker for Mn and other metals (Pb, Cr, Cu), using ICP-MS, scanning electron microscopy, and laser ablation ICP-MS to evaluate cleaning efficacy. Exogenous metal contamination on hair that was untreated or intentionally contaminated with dust or Mn-contaminated water was effectively removed using a cleaning method of 0.5% Triton X-100 sonication plus 1N nitric acid sonication. This cleaning method was then used on hair samples from children (n=121) in an ongoing study of environmental Mn exposure and related health effects. Mean hair Mn levels were 0.121 μg/g (median = 0.073 μg/g, range = 0.011 – 0.736 μg/g), which are ~4 to 70-fold lower than levels reported in other pediatric Mn studies. Hair Mn levels were also significantly higher in children living in the vicinity of active, but not historic, ferroalloy plant emissions compared to controls (P<0.001). These data show that exogenous metal contamination on hair can be effectively cleaned of exogenous metal contamination, and they substantiate the use of hair Mn levels as a biomarker of environmental Mn exposure in children. PMID:23259818

[Study on the determination of 28 inorganic elements in sunflower seeds by ICP-OES/ICP-MS].

PubMed

Liu, Hong-Wei; Qin, Zong-Hui; Xie, Hua-Lin; Cao, Shu

2013-01-01

The present paper describes a simple method for the determination of trace elements in sunflower seeds by using inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma spectrometry (ICP-MS). HNO3 + H2O2 were used to achieve the complete decomposition of the organic matrix in a closed-vessel microwave oven. The contents of 10 trace elements (Al, B, Ca, Fe, K, Mg, Na, Si, P and S) in sunflower seeds were determined by ICP-OES while 18 trace elements (As, Ba, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Rb, Sr, Sn, Sb, Ti, V and Zn) were determined by ICP-MS. The rice reference material (GBW10045) was used as standard reference materials. The results showed a good agreement between measured and certified values for all analytes. The concentrations of necessary micro elements Ca, K, Mg, P and S were higher. This method was simple, sensitive and precise and can perform simultaneous multi-elements determination of sunflower seeds.

Determination of Trace Elements in Uranium by HPLC-ID-ICP-MS: NTNFC Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manard, Benjamin Thomas; Wylie, Ernest Miller II; Xu, Ning

This report covers the FY 16 effort for the HPLC-ID-ICP-MS methodology 1) sub-method validation for the group I&II elements, 2) sub-method stood-up and validation for REE, 3) sub-method development for the transition element, and 4) completion of a comprehensive SOP for three families of elements.

The use of atomic spectroscopy in the pharmaceutical industry for the determination of trace elements in pharmaceuticals.

PubMed

Lewen, Nancy

2011-06-25

The subject of the analysis of various elements, including metals and metalloids, in the pharmaceutical industry has seen increasing importance in the last 10-15 years, as modern analytical instrumentation has afforded analysts with the opportunity to provide element-specific, accurate and meaningful information related to pharmaceutical products. Armed with toxicological data, compendial and regulatory agencies have revisited traditional approaches to the testing of pharmaceuticals for metals and metalloids, and analysts have begun to employ the techniques of atomic spectroscopy, such as flame- and graphite furnace atomic absorption spectroscopy (FAAS, Flame AA or FAA and GFAAS), inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS), to meet their analytical needs. Newer techniques, such as laser-induced breakdown spectroscopy (LIBS) and Laser Ablation ICP-MS (LAICP-MS) are also beginning to see wider applications in the analysis of elements in the pharmaceutical industry.This article will provide a perspective regarding the various applications of atomic spectroscopy in the analysis of metals and metalloids in drug products, active pharmaceutical ingredients (API's), raw materials and intermediates. The application of atomic spectroscopy in the analysis of metals and metalloids in clinical samples, nutraceutical, metabolism and pharmacokinetic samples will not be addressed in this work. Copyright © 2010 Elsevier B.V. All rights reserved.

Minerals and Trace Elements in Milk, Milk Products, Infant Formula, and Adult/Pediatric Nutritional Formula, ICP-MS Method: Collaborative Study, AOAC Final Action 2015.06, ISO/DIS 21424, IDF 243.

PubMed

Pacquette, Lawrence H; Thompson, Joseph J; Malaviole, I; Zywicki, R; Woltjes, F; Ding, Y; Mittal, A; Ikeuchi, Y; Sadipiralla, B; Kimura, S; Veltman, H; Miura, A

2018-03-01

AOAC Final Action Official MethodSM 2015.06 "Minerals and Trace Elements in Milk, Milk Products, Infant Formula and Adult/Pediatric Nutritional Formula, ICP-MS Method" was collaboratively studied. Note that "milk, milk products" has now been added to the title of the Final Action method because whole milk and several dairy ingredients were successfully incorporated into the collaborative study for the purpose of developing an International Organization for Standardization/International Dairy Federation standard (ISO/DIS 21424; in progress). The method determines sodium, magnesium, phosphorus, potassium, calcium, iron, manganese, zinc, copper, chromium, molybdenum, and selenium by inductively coupled plasma (ICP)-MS after microwave digestion. Ten laboratories participated in the study, and data from five different model ICP-MS units were represented. Thirteen products, five placebo products, and six dairy samples were tested as blind duplicates in this study, along with a standard reference material, for a total 50 samples. The overall repeatability and reproducibility for all samples met Standard Method Performance Requirements put forth by the AOAC Stakeholder Panel on Infant Formula and Adult Nutritionals, with a few exceptions. Comparisons are made to ICP-atomic emission data from a collaborative study of AOAC Official Method 2011.14 carried out concurrently on these same samples.

Synthesis of cross-linked chitosan modified with the glycine moiety for the collection/concentration of bismuth in aquatic samples for ICP-MS determination.

PubMed

Oshita, Koji; Noguchi, Osamu; Oshima, Mitsuko; Motomizu, Shoji

2007-10-01

A chelating resin, cross-linked chitosan modified with the glycine moiety (glycine-type chitosan resin), was developed for the collection and concentration of bismuth in aquatic samples for ICP-MS measurements. The adsorption behavior of bismuth and 55 elements on glycine-type chitosan resin was systematically examined by passing a sample solution containing 56 elements through a mini-column packed with the resin (wet volume; 1 ml). After eluting the elements adsorbed on the resin with nitric acid, the eluates were measured by ICP-MS. The glycine-type chitosan resin could adsorb several cations by a chelating mechanism and several oxoanions by an anion-exchange mechanism. Especially, the resin could adsorb almost 100% Bi(III) over a wide pH region from pH 2 to 6. Bismuth could be strongly adsorbed at pH 3, and eluted quantitatively with 10 ml of 3 M nitric acid. A column pretreatment method with the glycine-type chitosan resin was used prior to removal of high concentrations of matrices in a seawater sample and the preconcentration of trace bismuth in river water samples for ICP-MS measurements. The column pretreatment method was also applied to the determination of bismuth in real samples by ICP-MS. The LOD of bismuth was 0.1 pg ml(-1) by 10-fold column preconcentration for ICP-MS measurements. The analytical results for bismuth in sea and river water samples by ICP-MS were 22.9 +/- 0.5 pg ml(-1) (RSD, 2.2%) and 2.08 +/- 0.05 pg ml(-1) (RSD, 2.4%), respectively.

Boron Content of Some Foods Consumed in Istanbul, Turkey.

PubMed

Kuru, Ruya; Yilmaz, Sahin; Tasli, Pakize Neslihan; Yarat, Aysen; Sahin, Fikrettin

2018-04-14

The boron content was determined in 42 different foods consumed in Istanbul, Turkey. Eleven species of fruit, ten species of vegetable, eight species of food of animal origin, four species of grain, two species of nuts, two species of legume, and five other kinds of foods were included to this study. They were analyzed by two methods: Inductively coupled plasma mass spectrometry (ICP-MS) technique and carminic acid assay, and the results of two methods were also compared. Boron concentration in foods ranged between 0.06-37.2 mg/kg. Nuts had the highest boron content while foods of animal origin had the lowest. A strong correlation was found between the results of the carminic acid assay and the ICP-MS technique (p = 0.0001, Pearson correlation coefficient: r = 0.956). Bland Altman analysis also supported this correlation. ICP-MS is one of the most common, reliable, and powerful method for boron determination. The results of our study show that spectrophotometric carminic acid assay can provide similar results to ICP-MS, and the boron content in food materials can be also determined by spectrophotometric method.

On the condition of UO2 nuclear fuel irradiated in a PWR to a burn-up in excess of 110 MWd/kgHM

NASA Astrophysics Data System (ADS)

Restani, R.; Horvath, M.; Goll, W.; Bertsch, J.; Gavillet, D.; Hermann, A.; Martin, M.; Walker, C. T.

2016-12-01

Post-irradiation examination results are presented for UO2 fuel from a PWR fuel rod that had been irradiated to an average burn-up of 105 MWd/kgHM and showed high fission gas release of 42%. The radial distribution of xenon and the partitioning of fission gas between bubbles and the fuel matrix was investigated using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and electron probe microanalysis. It is concluded that release from the fuel at intermediate radial positions was mainly responsible for the high fission gas release. In this region thermal release had occurred from the high burn-up structure (HBS) at some point after the sixth irradiation cycle. The LA-ICP-MS results indicate that gas release had also occurred from the HBS in the vicinity of the pellet periphery. It is shown that the gas pressure in the HBS pores is well below the pressure that the fuel can sustain.

LA-ICP-MS and SIMS U-Pb and U-Th zircon geochronological data of Late Pleistocene lava domes of the Ciomadul Volcanic Dome Complex (Eastern Carpathians).

PubMed

Lukács, Réka; Guillong, Marcel; Schmitt, Axel K; Molnár, Kata; Bachmann, Olivier; Harangi, Szabolcs

2018-06-01

This article provides laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and secondary ionization mass spectrometry (SIMS) U-Pb and U-Th zircon dates for crystals separated from Late Pleistocene dacitic lava dome rocks of the Ciomadul Volcanic Dome Complex (Eastern Carpathians, Romania). The analyses were performed on unpolished zircon prism faces (termed rim analyses) and on crystal interiors exposed through mechanical grinding an polishing (interior analyses). 206 Pb/ 238 U ages are corrected for Th-disequilibrium based on published and calculated distribution coefficients for U and Th using average whole-rock and individually analyzed zircon compositions. The data presented in this article were used for the Th-disequilibrium correction of (U-Th)/He zircon geochronology data in the research article entitled "The onset of the volcanism in the Ciomadul Volcanic Dome Complex (Eastern Carpathians): eruption chronology and magma type variation" (Molnár et al., 2018) [1].

Geochemical differences of magnetite from the Algoma- and Superior- type banded iron formations based on in situ LA-ICP-MS analysis

NASA Astrophysics Data System (ADS)

Moon, I.; Lee, I.; Park, J. W.; Yang, X.

2017-12-01

Precambrian banded iron formations (BIFs) have been highly attractive study issues for decades about their genesis. Recently, more detailed geochemical studies have been conducted on mineral chemistry of magnetite using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Magnetite geochemistry enables us to constrain the physicochemical controlling factors for abundance of trace elements in magnetite and understand depositional environment of BIFs. In this study, we provide results of magnetite trace elemental features from two representative types of BIFs which are Algoma- and Superior- type BIF in the world, with aims to understand systematic differences in magnetite compositions between Algoma- and Superior- type BIF. The magnetites are divided into two groups according to their Al, Mn, Ti, V, and Ni concentration. The magnetites from the Algoma-type BIFs are more enriched in trace elements than those from the Superior-type. The geochemical differences are caused by difference precipitation condition including oxygen fugacity, temperature and fluid source.

A novel strategy to evaluate the degradation of quantum dots: identification and quantification of CdTe quantum dots and corresponding ionic species by CZE-ICP-MS.

PubMed

Meng, Peijun; Xiong, Yamin; Wu, Yingting; Hu, Yue; Wang, Hui; Pang, Yuanfeng; Jiang, Shuqing; Han, Sihai; Huang, Peili

2018-05-09

In view of the significance and urgency of the speciation analysis of quantum dots (QDs) and their degradation products for clarifying their degradation rules and toxicity mechanisms, a method for the identification and quantification of CdTe QDs and corresponding ionic species in complex matrices was developed using capillary zone electrophoresis (CZE) coupled to inductively coupled plasma-mass spectrometry (ICP-MS). The quality assessment of commercial CdTe QDs and serum pharmacokinetics of synthesized CdTe QDs in rats were successfully undertaken using the developed CZE-ICP-MS method.

Precise and traceable carbon isotope ratio measurements by multicollector ICP-MS: what next?

PubMed

Santamaria-Fernandez, Rebeca

2010-06-01

This article reviews recent developments in the use of multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) to provide high-precision carbon isotope ratio measurements. MC-ICP-MS could become an alternative method to isotope ratio mass spectrometry (IRMS) for rapid carbon isotope ratio determinations in organic compounds and characterisation and certification of isotopic reference materials. In this overview, the advantages, drawbacks and potential of the method for future applications are critically discussed. Furthermore, suggestions for future improvements in terms of precision and sensitivity are made. No doubt, this is an exciting analytical challenge and, as such, hurdles will need to be cleared.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dion, Michael P.; Liezers, Martin; Farmer, Orville T.

2015-01-01

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

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.

Improvements in Precise and Accurate Isotope Ratio Determination via LA-MC-ICP-MS by Application of an Alternative Data Reduction Protocol

NASA Astrophysics Data System (ADS)

Fietzke, J.; Liebetrau, V.; Guenther, D.; Frische, M.; Zumholz, K.; Hansteen, T. H.; Eisenhauer, A.

2008-12-01

An alternative approach for the evaluation of isotope ratio data using LA-MC-ICP-MS will be presented. In contrast to previously applied methods it is based on the simultaneous responses of all analyte isotopes of interest and the relevant interferences without performing a conventional background correction. Significant improvements in precision and accuracy can be achieved when applying this new method and will be discussed based on the results of two first methodical applications: a) radiogenic and stable Sr isotopes in carbonates b) stable chlorine isotopes of pyrohydrolytic extracts. In carbonates an external reproducibility of the 87Sr/86Sr ratios of about 19 ppm (RSD) was achieved, an improvement of about a factor of 5. For recent and sub-recent marine carbonates a mean radiogenic strontium isotope ratio 87Sr/86Sr of 0.709170±0.000007 (2SE) was determined, which agrees well with the value of 0.7091741±0.0000024 (2SE) reported for modern sea water [1,2]. Stable chlorine isotope ratios were determined ablating pyrohydrolytic extracts with a reproducibility of about 0.05‰ (RSD). For basaltic reference material JB1a and JB2 chlorine isotope ratios were determined relative to SMOC (standard mean ocean chlorinity) δ37ClJB-1a = (-0.99±0.06) ‰ and δ37ClJB-1a = (-0.60±0.03) ‰ (SD), respectively, in accordance with published data [3]. The described strategies for data reduction are considered to be generally applicable for all isotope ratio measurements using LA-MC-ICP-MS. [1] J.M. McArthur, D. Rio, F. Massari, D. Castradori, T.R. Bailey, M. Thirlwall, S. Houghton, Palaeogeo. Palaeoclim. Palaeoeco., 2006, 242 (126), doi: 10.1016/j.palaeo.2006.06.004 [2] J. Fietzke, V. Liebetrau, D. Guenther, K. Guers, K. Hametner, K. Zumholz, T.H. Hansteen and A. Eisenhauer, J. Anal. At. Spectrom., 2008, 23, 955-961, doi:10.1039/B717706B [3] J. Fietzke, M. Frische, T.H. Hansteen and A. Eisenhauer, J. Anal. At. Spectrom., 2008, 23, 769-772, doi:10.1039/B718597A

GHR1 - A new Eocene natural reference material for U-Pb and Hf isotopic measurements in zircon

NASA Astrophysics Data System (ADS)

Ibanez-Mejia, M.; Eddy, M. P.

2017-12-01

We present chemical abrasion-isotope dilution-thermal ionization (CA-ID-TIMS) U-Pb zircon geochronology and solution multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) Hf isotopic data from a proposed natural zircon reference material for use during in situ analyses of U-Pb and Hf isotopic ratios. The sample, GHR1, was collected from the rapakivi intrusive phase of the Eocene Golden Horn batholith in Washington, USA. Zircons separated from this sample range up to 250-300 μm in length and have moderate aspect ratios. A weighted mean of 15 Th-corrected 206Pb/238U zircon dates from GHR1 produced at the Massachusetts Institute of Technology is 48.132 ± 0.023 Ma (2σ analytical and tracer uncertainties only, MSWD=1.70) confirming that there is little or no inter-crystal age heterogeneity at the scale of a few 10 kyr. Solution MC-ICP-MS measurements of chemically purified aliquots give a 176Hf/177Hf weighted mean of 0.283050 ± 17 (2σ, n=10), corresponding to a ɛHf0 of ca. +9.3. The 2σ variability of these measurements is comparable to our reproducibility of the JMC-475 Hf isotopic standard 0.282160 ± 14 (n= 13), suggesting that GHR1 zircons are homogenous with respect to 176Hf/177Hf. In situ 206Pb/238U dates from collaborating secondary ion mass spectrometry (SIMS), sensitive high-resolution ion microprobe (SHRIMP), and laser ablation ICP-MS (LA-ICP-MS) laboratories are in excellent agreement with the CA-ID-TIMS date and illustrate the reproducibility and potential value of this reference zircon. The mean values of 176Hf/177Hf measurements from two LA-ICP-MS laboratories are in agreement with the solution MC-ICP-MS value, but show slightly greater dispersion and higher (Lu+Yb)/Hf values. We attribute this discrepancy to apatite inclusions that are high in REE and may lead to greater isobaric interferences on 176Hf. These inclusions and potential isobaric interferences from REE were removed during the chemical abrasion step prior to bulk dissolution and ion-exchange purification in the solution data. Nevertheless, the apparent isotopic homogeneity and reproducibility of 206Pb/238U and 176Hf/177Hf ratios and the potentially unlimited reserves of GHR1 suggest that it is a promising reference material. We plan to distribute GHR1 at the meeting to interested laboratories.

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

PubMed

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

2015-10-22

Wet-milling protocol was employed to produce pressed powder tablets with excellent cohesion and homogeneity suitable for laser ablation (LA) analysis of volatile and refractive elements in sediment. The influence of sample preparation on analytical performance was also investigated, including sample homogeneity, accuracy and limit of detection. Milling in volatile solvent for 40 min ensured sample is well mixed and could reasonably recover both volatile (Hg) and refractive (Zr) elements. With the exception of Cr (-52%) and Nb (+26%) major, minor and trace elements in STSD-1 and MESS-3 could be analysed within ±20% of the certified values. Comparison of the method with total digestion method using HF was tested by analysing 10 different sediment samples. The laser method recovers significantly higher amounts of analytes such as Ag, Cd, Sn and Sn than the total digestion method making it a more robust method for elements across the periodic table. LA-ICP-MS also eliminates the interferences from chemical reagents as well as the health and safety risks associated with digestion processes. Therefore, it can be considered as an enhanced method for the analysis of heterogeneous matrices such as river sediments. Copyright © 2015 Elsevier B.V. All rights reserved.

Biomonitoring of boron: Development and characterization of a simple, reliable and quality controlled biomonitoring method.

PubMed

Michalke, Bernhard

2017-03-01

Boron exposure is of interest and concern from an occupational point of view. Usual daily boron intake is related to boron blood plasma concentration <1mg/L and to <3mg/L in urine, but after exposure urine concentrations are quickly elevated. Reliable boron biomonitoring, typically in urine, thus is mandatory for occupational health control institutions. This paper reports on the development of a simple, fast and reliable boron determination procedure based on inductively coupled plasma - optical emission spectrometry (ICP-OES). Major aims for this method were simplicity in sample preparation, low risk for artifacts and interferences, high precision and accuracy, possibly low costs, including lower costs for element selective detection, short total analysis time and suitability for occupational health laboratories. Precision data (serial or day-to-day) from urine and doped urine were very good: <1.5 or <2%. Accuracy was calculated from analysis of a certified reference material (ERM-CD 281), as 99% or according to recoveries of doped concentrations ranging from 102 to 109% recovery. For cross-checking ICP-OES determinations, samples were analyzed also by quadrupole ICP-qMS and by sectorfield ICP-sf-MS at low and medium resolution. Both systems confirmed ICP-OES measurements when using 11 B for quantification. Determinations based on 10 B however showed some bias, except with ICP-sf-MS at medium resolution. The observed elevated signals are discussed with respect to the known Ne ++ interference (as an impurity in Ar), which is not separated in low resolving quadrupole ICP-MS systems or ICP-sf-MS at low resolution. Copyright © 2016 Elsevier GmbH. All rights reserved.

Metabolite profiling with HPLC-ICP-MS as a tool for in vivo characterization of imaging probes.

PubMed

Boros, Eszter; Pinkhasov, Omar R; Caravan, Peter

2018-01-01

Current analytical methods for characterizing pharmacokinetic and metabolic properties of positron emission tomography (PET) and single photon emission computed tomography (SPECT) probes are limited. Alternative methods to study tracer metabolism are needed. The study objective was to assess the potential of high performance liquid chromatography - inductively coupled plasma - mass spectrometry (HPLC-ICP-MS) for quantification of molecular probe metabolism and pharmacokinetics using stable isotopes. Two known peptide-DOTA conjugates were chelated with nat Ga and nat In. Limit of detection of HPLC-ICP-MS for 69 Ga and 115 In was determined. Rats were administered 50-150 nmol of Ga- and/or In-labeled probes, blood was serially sampled, and plasma analyzed by HPLC-ICP-MS using both reverse phase and size exclusion chromatography. The limits of detection were 0.16 pmol for 115 In and 0.53 pmol for 69 Ga. Metabolites as low as 0.001 %ID/g could be detected and transchelation products identified. Simultaneous administration of Ga- and In-labeled probes allowed the determination of pharmacokinetics and metabolism of both probes in a single animal. HPLC-ICP-MS is a robust, sensitive and radiation-free technique to characterize the pharmacokinetics and metabolism of imaging probes.

Metal dispersion and transportational activities using food crops as biomonitors.

PubMed

Ward, N I; Savage, J M

1994-05-23

The multielement (Al, Ca, Cd, Ce, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Si, and Zn) levels of various common vegetables (bean, broccoli, cabbage, cauliflower, lettuce, marrow, onion, parsnip, spinach, sprouts, sweet corn, and tomato); fruits (grape and strawberry); herbs (garlic, lemon balm, marjoram, mint, rosemary and tarragon); local pasture species and surface soils collected from a commercial garden centre located within a distance of 30 m of the London Orbital Motorway (M25) is presented. Comparative values are given from a background area, namely a domestic garden located in the North Yorkshire Dales National Park area. Analysis was undertaken by inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma-source mass spectrometry (ICP-MS) with quality control assessment using four international biological reference materials; BCR:CRM 62 Olive Leaves, NIST 1575 Pine Needles, NIST 1573 Tomato Leaves, and NIST 1572 Citrus Leaves. Inter-analytical method comparison is given using two methods of ICP-MS; namely conventional pneumatic nebulisation of sample solution, and direct solids analysis by laser ablation; and neutron activation analysis methods (NAA). For the elements listed there is a good precision obtained by ICP-MS and NAA. In particular levels of < +/- 1-10% (rsd) are obtained. Comparison of data with certified values and other analytical methods are generally of very good agreement. Lead levels in background areas ranged from 0.0008 to 0.340 microgram/g (fresh weight) for plant material; with the lead magnitude greater for grasses > herbs > vegetables > cereals > fruits. Measured values are in good agreement with reported literature values. The lowest Pb values are for marrow, lettuce, tomato and sweet corn samples (approximately 0.001-0.021 microgram/g). 'Green' leaf material levels were approximately 0.02-0.10 microgram/g (i.e. sprouts and cabbage). Root vegetables contain higher levels, approximately 0.02-0.125 microgram/g (especially carrot), reflecting possible metal uptake from soil. The highest vegetable Pb values are for leek and onion (approximately 0.35 microgram/g). Background values are also provided for nineteen elements (Al, As, B, Ba, Br, Cd, Co, Cr, Cu, Fe, Li, Mn, Mo, Ni, Rb, Se, Sr, V, and Zn). Exposure to motor vehicle activities at a site some 30 m from the M25 shows only significant increases in Pb for unwashed plant material and surface soils. Typically Pb levels of 40-80% can be removed by washing plant surfaces resulting in metal levels similar to background areas.(ABSTRACT TRUNCATED AT 400 WORDS)

Petrochronology in constraining early Archean Earth processes and environments: Barberton greenstone belt, South Africa

NASA Astrophysics Data System (ADS)

Grosch, Eugene

2017-04-01

Analytical and petrological software developments over the past decade have seen rapid innovation in high-spatial resolution petrological techniques, for example, laser-ablation ICP-MS, secondary ion microprobe (SIMS, nano-SIMS), thermodynamic modelling and electron microprobe microscale mapping techniques (e.g. XMapTools). This presentation will focus on the application of petrochronology to ca. 3.55 to 3.33 billion-year-old metavolcanic and sedimentary rocks of the Onverwacht Group, shedding light on the earliest geologic evolution of the Paleoarchean Barberton greenstone belt (BGB) of South Africa. The field, scientific drilling and petrological research conducted over the past 8 years, aims to illustrate how: (a) LA-ICP-MS and SIMS U-Pb detrital zircon geochronology has helped identify the earliest tectono-sedimentary basin and sediment sources in the BGB, as well as reconstructing geodynamic processes as early as ca. 3.432 billion-years ago; (b) in-situ SIMS multiple sulphur isotope analysis of sulphides across various early Archean rock units help to reconstruct atmospheric, surface and subsurface environments on early Archean Earth and (c) the earliest candidate textural traces for subsurface microbial life can be investigated by in-situ LA-ICP-MS U-Pb dating of titanite, micro-XANES Fe-speciation analysis and metamorphic microscale mapping. Collectively, petrochronology combined with high-resolution field mapping studies, is a powerful multi-disciplinary approach towards deciphering petrogenetic and geodynamic processes preserved in the Paleoarchean Barberton greenstone belt of South Africa, with implications for early Archean Earth evolution.

Assessment and forensic application of laser-induced breakdown spectroscopy (LIBS) for the discrimination of Australian window glass.

PubMed

El-Deftar, Moteaa M; Speers, Naomi; Eggins, Stephen; Foster, Simon; Robertson, James; Lennard, Chris

2014-08-01

A commercially available laser-induced breakdown spectroscopy (LIBS) instrument was evaluated for the determination of elemental composition of twenty Australian window glass samples, consisting of 14 laminated samples and 6 non-laminated samples (or not otherwise specified) collected from broken windows at crime scenes. In this study, the LIBS figures of merit were assessed in terms of accuracy, limits of detection and precision using three standard reference materials (NIST 610, 612, and 1831). The discrimination potential of LIBS was compared to that obtained using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), X-ray microfluorescence spectroscopy (μXRF) and scanning electron microscopy energy dispersive X-ray spectrometry (SEM-EDX) for the analysis of architectural window glass samples collected from crime scenes in the Canberra region, Australia. Pairwise comparisons were performed using a three-sigma rule, two-way ANOVA and Tukey's HSD test at 95% confidence limit in order to investigate the discrimination power for window glass analysis. The results show that the elemental analysis of glass by LIBS provides a discrimination power greater than 97% (>98% when combined with refractive index data), which was comparable to the discrimination powers obtained by LA-ICP-MS and μXRF. These results indicate that LIBS is a feasible alternative to the more expensive LA-ICP-MS and μXRF options for the routine forensic analysis of window glass samples. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Trace metal analysis by laser ablation-inductively coupled plasmamass spectrometry and x-ray K-edge densitometry of forensic samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berry, Jonna Elizabeth

This dissertation describes a variety of studies on the determination of trace elements in samples with forensic importance. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to determine the trace element composition of numerous lipstick samples. Lipstick samples were determined to be homogeneous. Most lipstick samples of similar colors were readily distinguishable at a 95% confidence interval based on trace element composition. Numerous strands of a multi-strand speaker cable were analyzed by LA-ICP-MS. The strands in this study are spatially heterogeneous in trace element composition. In actual forensic applications, the possibility of spatial heterogeneity must be considered, especially in casesmore » where only small samples (e.g., copper wire fragments after an explosion) are available. The effects of many unpredictable variables, such as weather, temperature, and human activity, on the retention of gunshot residue (GSR) around projectile wounds were assessed with LAICP- MS. Skin samples around gunshot and stab wounds and larvae feeding in and around the wounds on decomposing pig carcasses were analyzed for elements consistent with GSR (Sb, Pb, Ba, and Cu). These elements were detected at higher levels in skin and larvae samples around the gunshot wounds compared to the stab wounds for an extended period of time throughout decomposition in both a winter and summer study. After decomposition, radiographic images of the pig bones containing possible damage from bullets revealed metallic particles embedded within a number of bones. Metallic particles within the bones were analyzed with x-ray, K-edge densitometry and determined to contain lead, indicating that bullet residue can be retained throughout decomposition and detected within bones containing projectile trauma.« less

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

Compared to non-destructive geochemical analyses, LA-ICP-MS consumes ca. 0.1 μm of material per ablation pulse. It is therefore to be expected that the combined analyses of ca. 200 pulses will encounter geochemical and isotopic complexities in all but the most perfect minerals. Experienced LA-ICP-MS analysts spot down-hole complexities and choose signal integration areas accordingly. In U-Pb geochronology, the task of signal integration choice is complex as the analyst wants to avoid areas of common Pb and Pb-loss and separate true (concordant) age complexity. Petrus and Kamber (2012) developed VizualAge as a tool for reducing and visualising, in real time, U-Pb geochronology data obtained by LA-ICP-MS as an add-on for the freely available U-Pb geochronology data reduction scheme of Paton et al. (2010) in Iolite. The most important feature of VizualAge is its ability to display a live concordia diagram, allowing users to inspect the data of a signal on a concordia diagram as the integration area it is being adjusted, thus providing immediate visual feedback regarding discordance, uncertainty, and common lead for different regions of the signal. It can also be used to construct histograms and probability distributions, standard and Tera-Wasserburg style concordia diagrams, as well as 3D U-Th-Pb and total U-Pb concordia diagrams. More recently, Chew et al. (2014) presented a new data reduction scheme (VizualAge_UcomPbine) with much improved common Pb correction functionality. Common Pb is a problem for many U-bearing accessory minerals and an under-appreciated difficulty is the potential presence of (possibly unevenly distributed) common Pb in calibration standards, introducing systematic inaccuracy into entire datasets. One key feature of the new method is that it can correct for variable amounts of common Pb in any U-Pb accessory mineral standard as long as the standard is concordant in the U/Pb (and Th/Pb) systems after common Pb correction. Common Pb correction can be undertaken using either the 204Pb, 207Pb or 208Pb(no Th) methods. After common Pb correction to the user-selected age standard integrations, the scheme fits session-wide model U-Pb fractionation curves to the time-resolved U-Pb standard data. This down hole fractionation model is next applied to the unknowns and sample-standard bracketing (using a user specified interpolation method) is used to calculate final isotopic ratios and ages. 204Pb- and 208Pb(no Th)-corrected concordia diagrams and 204Pb-, 207Pb- and 208Pb(no Th)-corrected age channels can be calculated for user-specified initial Pb ratio(s). All other conventional common Pb correction methods (e.g. intercept or isochron methods on co-genetic analyses) can be performed offline. Apatite, titanite, rutile and very young zircon data will be presented, obtained using a Thermo Scientific iCAP-Qc (Q-ICP-MS) coupled to a Photon Machines Analyte Excite 193 nm ArF Excimer laser with a novel signal smoothing device Chew, D.M., Petrus, J.A., and Kamber, B.S. (2014); Chemical Geology, 363, 185-199. Paton C., Woodhead J.D., Hellstrom J.C., Hergt J.M., Greig A. and Maas R. (2010); Geochemistry Geophysics Geosystems, 11, 1-36. Petrus, J.A. and Kamber, B.S. (2012): Geostandards and Geoanalytical Research, 36, 247-270.

40 CFR Table 2 to Subpart Llll of... - Emission Limits and Standards for New Multiple Hearth Sewage Sludge Incineration Units

Code of Federal Regulations, 2013 CFR

2013-07-01

... meters per run) Performance test (Method 29 at 40 CFR part 60, appendix A-8). Use GFAAS or ICP/MS for the...-8. Use GFAAS or ICP/MS for the analytical finish. Fugitive emissions from ash handling Visible...

40 CFR Table 2 to Subpart Llll of... - Emission Limits and Standards for New Multiple Hearth Sewage Sludge Incineration Units

Code of Federal Regulations, 2014 CFR

2014-07-01

... meters per run) Performance test (Method 29 at 40 CFR part 60, appendix A-8). Use GFAAS or ICP/MS for the...-8. Use GFAAS or ICP/MS for the analytical finish. Fugitive emissions from ash handling Visible...

Accurate determination of non-metallic impurities in high purity tetramethylammonium hydroxide using inductively coupled plasma tandem mass spectrometry

NASA Astrophysics Data System (ADS)

Fu, Liang; Xie, Hualin; Shi, Shuyun; Chen, Xiaoqing

2018-06-01

The content of non-metallic impurities in high-purity tetramethylammonium hydroxide (HPTMAH) aqueous solution has an important influence on the yield, electrical properties and reliability of the integrated circuit during the process of chip etching and cleaning. Therefore, an efficient analytical method to directly quantify the content of non-metallic impurities in HPTMAH aqueous solutions is necessary. The present study was aimed to develop a novel method that can accurately determine seven non-metallic impurities (B, Si, P, S, Cl, As, and Se) in an aqueous solution of HPTMAH by inductively coupled plasma tandem mass spectrometry (ICP-MS/MS). The samples were measured using a direct injection method. In the MS/MS mode, oxygen and hydrogen were used as reaction gases in the octopole reaction system (ORS) to eliminate mass spectral interferences during the analytical process. The detection limits of B, Si, P, S, Cl, As, and Se were 0.31, 0.48, 0.051, 0.27, 3.10, 0.008, and 0.005 μg L-1, respectively. The samples were analyzed by the developed method and the sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) was used for contrastive analysis. The values of these seven elements measured using ICP-MS/MS were consistent with those measured by SF-ICP-MS. The proposed method can be utilized to analyze non-metallic impurities in HPTMAH aqueous solution. Table S2 Multiple potential interferences on the analytes. Table S3 Parameters of calibration curve and the detection limit (DL). Table S4 Results obtained for 25% concentration high-purity grade TMAH aqueous solution samples (μg L-1, mean ± standard deviation, n = 10).

Molecules and elements for quantitative bioanalysis: The allure of using electrospray, MALDI, and ICP mass spectrometry side-by-side.

PubMed

Linscheid, Michael W

2018-03-30

To understand biological processes, not only reliable identification, but quantification of constituents in biological processes play a pivotal role. This is especially true for the proteome: protein quantification must follow protein identification, since sometimes minute changes in abundance tell the real tale. To obtain quantitative data, many sophisticated strategies using electrospray and MALDI mass spectrometry (MS) have been developed in recent years. All of them have advantages and limitations. Several years ago, we started to work on strategies, which are principally capable to overcome some of these limits. The fundamental idea is to use elemental signals as a measure for quantities. We began by replacing the radioactive 32 P with the "cold" natural 31 P to quantify modified nucleotides and phosphorylated peptides and proteins and later used tagging strategies for quantification of proteins more generally. To do this, we introduced Inductively Coupled Plasma Mass Spectrometry (ICP-MS) into the bioanalytical workflows, allowing not only reliable and sensitive detection but also quantification based on isotope dilution absolute measurements using poly-isotopic elements. The detection capability of ICP-MS becomes particularly attractive with heavy metals. The covalently bound proteins tags developed in our group are based on the well-known DOTA chelate complex (1,4,7,10-tetraazacyclododecane-N,N',N″,N‴-tetraacetic acid) carrying ions of lanthanoides as metal core. In this review, I will outline the development of this mutual assistance between molecular and elemental mass spectrometry and discuss the scope and limitations particularly of peptide and protein quantification. The lanthanoide tags provide low detection limits, but offer multiplexing capabilities due to the number of very similar lanthanoides and their isotopes. With isotope dilution comes previously unknown accuracy. Separation techniques such as electrophoresis and HPLC were used and just slightly adapted workflows, already in use for quantification in bioanalysis. Imaging mass spectrometry (MSI) with MALDI and laser ablation ICP-MS complemented the range of application in recent years. © 2018 Wiley Periodicals, Inc.

Urinary iodine: comparison of a simple method for its determination in microplates with measurement by inductively-coupled plasma mass spectrometry

PubMed Central

Haap, Michael; Roth, Heinz Jürgen; Huber, Thomas; Dittmann, Helmut; Wahl, Richard

2017-01-01

The aim of our study was to develop and validate an inexpensive, rapid, easy to use quantitative method to determine urinary iodine without major procurement costs for equipment. The rationale behind introducing this method is the increasing demand for urinary iodine assessments. Our study included 103 patients (76 female, 27 male), age (arithmetic mean) 52 ± 17.3 years. Urinary iodine was determined in microplates by a modification of the Sandell-Kolthoff reaction. The results were compared with inductively-coupled plasma mass spectrometry (ICP-MS) for iodine, considered as reference method. Geometric mean of urinary iodine determined by the Sandell-Kolthoff reaction method was 62.69 μg/l (95% confidence interval 53.16–73.92) whereas by the ICP-MS method it was 65.53 μg/l (95% confidence interval 54.77–78.41). Passing-Bablok regression equations for both methods gave y = 3.374 + 0.873x (y: Sandell-Kolthoff method, x: ICP-MS). Spearman´s correlation coefficient was 0.981, indicating a very high degree of agreement between the two methods. Bland-Altman plots showed no significant systematic difference between the two methods. The modified Sandell-Kolthoff method using microtiter plate technique presented here is a simple, inexpensive semi-automated method to determine urinary iodine with very little toxic waste. Comparison with the ICP-MS-technique yielded a good agreement between the two methods. PMID:28045077

Determination of phosphorus in small amounts of protein samples by ICP-MS.

PubMed

Becker, J Sabine; Boulyga, Sergei F; Pickhardt, Carola; Becker, J; Buddrus, Stefan; Przybylski, Michael

2003-02-01

Inductively coupled plasma mass spectrometry (ICP-MS) is used for phosphorus determination in protein samples. A small amount of solid protein sample (down to 1 micro g) or digest (1-10 micro L) protein solution was denatured in nitric acid and hydrogen peroxide by closed-microvessel microwave digestion. Phosphorus determination was performed with an optimized analytical method using a double-focusing sector field inductively coupled plasma mass spectrometer (ICP-SFMS) and quadrupole-based ICP-MS (ICP-QMS). For quality control of phosphorus determination a certified reference material (CRM), single cell proteins (BCR 273) with a high phosphorus content of 26.8+/-0.4 mg g(-1), was analyzed. For studies on phosphorus determination in proteins while reducing the sample amount as low as possible the homogeneity of CRM BCR 273 was investigated. Relative standard deviation and measurement accuracy in ICP-QMS was within 2%, 3.5%, 11% and 12% when using CRM BCR 273 sample weights of 40 mg, 5 mg, 1 mg and 0.3 mg, respectively. The lowest possible sample weight for an accurate phosphorus analysis in protein samples by ICP-MS is discussed. The analytical method developed was applied for the analysis of homogeneous protein samples in very low amounts [1-100 micro g of solid protein sample, e.g. beta-casein or down to 1 micro L of protein or digest in solution (e.g., tau protein)]. A further reduction of the diluted protein solution volume was achieved by the application of flow injection in ICP-SFMS, which is discussed with reference to real protein digests after protein separation using 2D gel electrophoresis.The detection limits for phosphorus in biological samples were determined by ICP-SFMS down to the ng g(-1) level. The present work discusses the figure of merit for the determination of phosphorus in a small amount of protein sample with ICP-SFMS in comparison to ICP-QMS.

A candidate reference method using ICP-MS for sweat chloride quantification.

PubMed

Collie, Jake T; Massie, R John; Jones, Oliver A H; Morrison, Paul D; Greaves, Ronda F

2016-04-01

The aim of the study was to develop a method for sweat chloride (Cl) quantification using Inductively Coupled Plasma Mass Spectrometry (ICP-MS) to present to the Joint Committee for Traceability in Laboratory Medicine (JCTLM) as a candidate reference method for the diagnosis of cystic fibrosis (CF). Calibration standards were prepared from sodium chloride (NaCl) to cover the expected range of sweat Cl values. Germanium (Ge) and scandium (Sc) were selected as on-line (instrument based) internal standards (IS) and gallium (Ga) as the off-line (sample based) IS. The method was validated through linearity, accuracy and imprecision studies as well as enrolment into the Royal College of Pathologists of Australasia Quality Assurance Program (RCPAQAP) for sweat electrolyte testing. Two variations of the ICP-MS method were developed, an on-line and off-line IS, and compared. Linearity was determined up to 225 mmol/L with a limit of quantitation of 7.4 mmol/L. The off-line IS demonstrated increased accuracy through the RCPAQAP performance assessment (CV of 1.9%, bias of 1.5 mmol/L) in comparison to the on-line IS (CV of 8.0%, bias of 3.8 mmol/L). Paired t-tests confirmed no significant differences between sample means of the two IS methods (p=0.53) or from each method against the RCPAQAP target values (p=0.08 and p=0.29). Both on and off-line IS methods generated highly reproducible results and excellent linear comparison to the RCPAQAP target results. ICP-MS is a highly accurate method with a low limit of quantitation for sweat Cl analysis and should be recognised as a candidate reference method for the monitoring and diagnosis of CF. Laboratories that currently practice sweat Cl analysis using ICP-MS should include an off-line IS to help negate any pre-analytical errors.

Comparison of ion chromatographic methods based on conductivity detection, post-column-reaction and on-line-coupling IC-ICP-MS for the determination of bromate.

PubMed

Schminke, G; Seubert, A

2000-02-01

An established method for the determination of the disinfection by-product bromate is ion chromatography (IC). This paper presents a comparison of three IC methods based on either conductivity detection (IC-CD), a post-column-reaction (IC-PCR-VIS) or the on-line-coupling with inductively coupled plasma mass spectrometry (IC-ICP-MS). Main characteristics of the methods such as method detection limits (MDL), time of analysis and sample pretreatment are compared and applicability for routine analysis is critically discussed. The most sensitive and rugged method is IC-ICP-MS, followed by IC-PCR-VIS. The photometric detection is subject to a minor interference in real world samples, presumably caused by carbonate. The lowest sensitivity is shown by the IC-CD method as slowest method compared, which, in addition, requires a sample pretreatment. The highest amount of information is delivered by IC-PCR-VIS, which allows the simultaneous determination of the seven standard anions and bromate.

Oxygen isotope geochemistry of Laurentide ice-sheet meltwater across Termination I

NASA Astrophysics Data System (ADS)

Vetter, Lael; Spero, Howard J.; Eggins, Stephen M.; Williams, Carlie; Flower, Benjamin P.

2017-12-01

We present a new method that quantifies the oxygen isotope geochemistry of Laurentide ice-sheet (LIS) meltwater across the last deglaciation, and reconstruct decadal-scale variations in the δ18O of LIS meltwater entering the Gulf of Mexico between ∼18 and 11 ka. We employ a technique that combines laser ablation ICP-MS (LA-ICP-MS) and oxygen isotope analyses on individual shells of the planktic foraminifer Orbulina universa to quantify the instantaneous δ18Owater value of Mississippi River outflow, which was dominated by meltwater from the LIS. For each individual O. universa shell, we measure Mg/Ca (a proxy for temperature) and Ba/Ca (a proxy for salinity) with LA-ICP-MS, and then analyze the same O. universa for δ18O using the remaining material from the shell. From these proxies, we obtain δ18Owater and salinity estimates for each individual foraminifer. Regressions through data obtained from discrete core intervals yield δ18Ow vs. salinity relationships with a y-intercept that corresponds to the δ18Owater composition of the freshwater end-member. Our data suggest that from 15.5 through 14.6 ka, estimated δ18Ow values of Mississippi River discharge from discrete core intervals range from -11‰ to -21‰ VSMOW, which is consistent with δ18O values from both regional precipitation and the low-elevation, southern margin of the LIS. During the Bølling and Allerød (14.0 through 13.3 ka), estimated δ18Ow values of Mississippi River discharge from discrete core intervals range from -22‰ to -38‰ VSMOW. These values suggest a dynamic melting history of different parts of the LIS, with potential contributions to Mississippi River outflow from both the low-elevation, southern margin of the LIS and high-elevation, high-latitude domes in the LIS interior that were transported to the ablation zone. Prior to ∼15.5 ka, the δ18Owater value of the Mississippi River was similar to that of regional precipitation or low-latitude LIS meltwater, but the Ba concentration in the Mississippi basin was affected by changes in weathering within the watershed, complicating Ba-salinity relationships in the Gulf of Mexico. After 13 ka, our data suggest Mississippi River outflow did not influence surface salinity above our Gulf of Mexico Orca Basin core site. Rather, we hypothesize that open ocean conditions prevailed as sea level rose and the paleoshoreline at the southern edge of North America retreated northward.

Application of ICP-MS and HPLC-ICP-MS for diagnosis and therapy of a severe intoxication with hexavalent chromium and inorganic arsenic.

PubMed

Heitland, Peter; Blohm, Martin; Breuer, Christian; Brinkert, Florian; Achilles, Eike Gert; Pukite, Ieva; Köster, Helmut Dietrich

2017-05-01

ICP-MS and HPLC-ICP-MS were applied for diagnosis and therapeutic monitoring in a severe intoxication with a liquid containing hexavalent chromium (Cr(VI)) and inorganic arsenic (iAs). In this rare case a liver transplantation of was considered as the only chance of survival. We developed and applied methods for the determination of Cr(VI) in erythrocytes and total chromium (Cr) and arsenic (As) in blood, plasma, urine and liver tissue by ICP-MS. Exposure to iAs was diagnosed by determination of iAs species and their metabolites in urine by anion exchange HPLC-ICP-MS. Three days after ingestion of the liquid the total Cr concentrations were 2180 and 1070μg/L in whole blood and plasma, respectively, and 4540μg/L Cr(VI) in erythrocytes. The arsenic concentration in blood was 206μg/L. The urinary As species concentrations were <0.5, 109, 115, 154 and 126μg/L for arsenobetaine, As(III), As(V), methylarsonate (V) and dimethylarsinate (V), respectively. Total Cr and As concentrations in the explanted liver were 11.7 and 0.9mg/kg, respectively. Further analytical results of this case study are tabulated and provide valuable data for physicians and toxicologists. Copyright © 2017. Published by Elsevier GmbH.

The influence of room temperature on Mg isotope measurements by MC-ICP-MS.

PubMed

Zhang, Xing-Chao; Zhang, An-Yu; Zhang, Zhao-Feng; Huang, Fang; Yu, Hui-Min

2018-03-24

We observed that the accuracy and precision of magnesium (Mg) isotope analyses could be affected if the room temperature oscillated during measurements. To achieve high quality Mg isotopic data, it is critical to evaluate how the unstable room temperature affects Mg isotope measurements by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We measured the Mg isotopes for the reference material DSM-3 using MC-ICP-MS under oscillating room temperatures in spring. For a comparison, we also measured the Mg isotopes under stable room temperatures, which was achieved by the installation of an improved temperature control system in the laboratory. The δ 26 Mg values measured under oscillating room temperatures have a larger deviation (δ 26 Mg from -0.09 to 0.08‰, with average δ 26 Mg = 0.00 ± 0.08 ‰) than those measured under a stable room temperature (δ 26 Mg from -0.03 to 0.03‰, with average δ 26 Mg = 0.00 ± 0.02 ‰) using the same MC-ICP-MS system. The room temperature variation can influence the stability of MC-ICP-MS. Therefore, it is critical to keep the room temperature stable to acquire high precise and accurate isotopic data when using MC-ICP-MS, especially when using the sample-standard bracketing (SSB) correction method. This article is protected by copyright. All rights reserved.

[Determination of heavy metals in four traditional Chinese medicines by ICP-MS].

PubMed

Wen, Hui-Min; Chen, Xiao-Hui; Dong, Ting-Xia; Zhan, Hua-Qiang; Bi, Kai-Shun

2006-08-01

To establish a ICP-MS method for the determination of heavy metals, including As, Hg, Pb, Cd, in four traditional Chinese medicines. The samples were digested by closed-versel microwave. The four heavy metals were directly analyzed by ICP-MS. Select internal standard element in for the method by which the analyse signal drife is corrected by the signal of another element (internal standard elements) added to both the standard solution and sample. For all of the analyzed heary methals, the correlative coefficient of the calibration curves was over 0.999 2. The recovery rates of the procedure were 97.5%-108.0%, and its RSD was lower than 11.6%. This method was convenient, quick-acquired, accurate and highly sensitive. The method can be used for the quality control of trace elements in traditional Chinese medicines and for the contents determination of traditional Chinese medicines from different habitats and species.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2009-10-01

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

40 CFR Table 1 to Subpart Llll of... - Emission Limits and Standards for New Fluidized Bed Sewage Sludge Incineration Units

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 CFR part 60, appendix A-8). Use GFAAS or ICP/MS for the analytical finish. Lead 0.00062 milligrams... per run) Performance test (Method 29 at 40 CFR part 60, appendix A-8. Use GFAAS or ICP/MS for the...

40 CFR Table 1 to Subpart Llll of... - Emission Limits and Standards for New Fluidized Bed Sewage Sludge Incineration Units

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 CFR part 60, appendix A-8). Use GFAAS or ICP/MS for the analytical finish. Lead 0.00062 milligrams... per run) Performance test (Method 29 at 40 CFR part 60, appendix A-8. Use GFAAS or ICP/MS for the...

Interrogating the variation of element masses and distribution patterns in single cells using ICP-MS with a high efficiency cell introduction system.

PubMed

Wang, Hailong; Wang, Meng; Wang, Bing; Zheng, Lingna; Chen, Hanqing; Chai, Zhifang; Feng, Weiyue

2017-02-01

Cellular heterogeneity is an inherent condition of cell populations, which results from stochastic expression of genes, proteins, and metabolites. The heterogeneity of individual cells can dramatically influence cellular decision-making and cell fate. So far, our knowledge about how the variation of endogenous metals and non-metals in individual eukaryotic cells is limited. In this study, ICP-MS equipped with a high efficiency cell introduction system (HECIS) was developed as a method of single-cell ICP-MS (SC-ICP-MS). The method was applied to the single-cell analysis of Mn, Fe, Co, Cu, Zn, P, and S in human cancer cell lines (HeLa and A549) and normal human bronchial epithelial cell line (16HBE). The analysis showed obvious variation of the masses of Cu, Fe, Zn, and P in individual HeLa cells, and variation of Fe, Zn, and P in individual A549 cells. On the basis of the single-cell data, a multimodal distribution of the elements in the cell population was fitted, which showed marked differences among the various cell lines. Importantly, subpopulations of the elements were found in the cell populations, especially in the HeLa cancer cells. This study demonstrates that SC-ICP-MS is able to unravel the extent of variation of endogenous elements in individual cells, which will help to improve our fundamental understanding of cellular biology and reveal novel insights into human biology and medicine. Graphical abstract The variations of masses and distribution patterns of elements Mn, Fe, Co, Cu, Zn, P, and S in single cells were successfully detected by ICP-MS coupled with a high efficiency cell introduction system (HECIS).

Implementation of bioassay methods to improve assessment of incorporated radionuclides.

PubMed

Oeh, U; Andrasi, A; Bouvier-Capely, C; De Carlan, L; Fischer, H; Franck, D; Höllriegl, V; Li, W B; Ritt, J; Roth, P; Schmitzer, Ch; Wahl, W; Zombori, P

2007-01-01

The present work which was carried out in the framework of an EU project (IDEA: Internal Dosimetry-Enhancements in Application; Contract Number: FIKR CT2001 00164) shall provide commonly acceptable guidelines for optimum performance of ICP-MS measurements with focus on urinary measurements of uranium, thorium and actinides. From the results of this work it is recommended that, whenever feasible, 24 h urine sampling should be conducted to avoid large uncertainties in the quantitation of daily urinary excretion values. For storage, urine samples should be acidified and kept frozen before analysis. Measurement of total uranium in urine by ICP-MS at physiological levels (<10 ng.l(-1)) requires no sample preparation besides UV photolysis and/or dilution. For the measurement of thorium in urine by ICP-MS, it can be concluded, that salt removal from the urine samples is not recommended. For the measurement of actinides in urine it is shown that ICP-MS is well-suited and a good alternative to alpha-spectrometry for isotopes with T1/2>5x10(4) years. In general, ICP-MS measurements are an easy, fast and cost-saving methodology. New improved measuring techniques (HR-SF-ICP-MS) with detection limits in urine of 150 pg.l(-1) (1.9 microBq.l(-1)) for 238U, 30 pg.l(-1) (2.4 microBq.l(-1)) for 235U and 100 pg.l(-1) (0.4 microBq.l(-1)) for (232)Th, respectively, meet all necessary requirements. This method should therefore become the routine technique for incorporation monitoring of workers and of members of the general public, in particular for uranium contamination.

The separation of 99Tc from low and medium-level radioactive wastes and its determination by inductively coupled plasma mass spectrometry.

PubMed

Hepiegne, P; Dall'ava, D; Clement, R; Degros, J P

1995-06-01

A chemical separation method has been developed for the determination of (99)Tc in various types of radioactive wastes. Such a method includes (i) fusion with NaOH, (ii) extraction in a column containing methyltrioctylammonium chloride, (iii) extraction by solvent with N-benzoyl-N-phenylhydroxylamine and, (iv) measurement by inductively-coupled plasma mass spectrometry (ICP-MS). From the performance standpoint, the recovery of (99)Tc, using (99m)Tc as a yield tracer, is higher than 70%. This analytical method, as developed, ensures effective decontamination with respect to the radionuclides, insofar the decontamination factors are greater than 10(+5), whenever the residual activity may be measured. Taking into account a 3sigma counting error, the detection limit obtained with the ICP-MS technique is 1.9 mBq/ml; the method enabling hence to detect activities as low as 0.3 Bq/g, with analysed samples of 0.2 g and a radiochemical yield of 70%. Studies have been dedicated to the (99)Tc measurement, using the electrothermal vaporization ICP-MS technique, which lowers the detection limit by a factor 10, with the standard solution (0.3 pg/ml), compared with the previous ICP-MS technique.

An integrated analysis for determining the geographical origin of medicinal herbs using ICP-AES/ICP-MS and (1)H NMR analysis.

PubMed

Kwon, Yong-Kook; Bong, Yeon-Sik; Lee, Kwang-Sik; Hwang, Geum-Sook

2014-10-15

ICP-MS and (1)H NMR are commonly used to determine the geographical origin of food and crops. In this study, data from multielemental analysis performed by ICP-AES/ICP-MS and metabolomic data obtained from (1)H NMR were integrated to improve the reliability of determining the geographical origin of medicinal herbs. Astragalus membranaceus and Paeonia albiflora with different origins in Korea and China were analysed by (1)H NMR and ICP-AES/ICP-MS, and an integrated multivariate analysis was performed to characterise the differences between their origins. Four classification methods were applied: linear discriminant analysis (LDA), k-nearest neighbour classification (KNN), support vector machines (SVM), and partial least squares-discriminant analysis (PLS-DA). Results were compared using leave-one-out cross-validation and external validation. The integration of multielemental and metabolomic data was more suitable for determining geographical origin than the use of each individual data set alone. The integration of the two analytical techniques allowed diverse environmental factors such as climate and geology, to be considered. Our study suggests that an appropriate integration of different types of analytical data is useful for determining the geographical origin of food and crops with a high degree of reliability. Copyright © 2014 Elsevier Ltd. All rights reserved.

Qualitative and quantitative spectro-chemical analysis of dates using UV-pulsed laser induced breakdown spectroscopy and inductively coupled plasma mass spectrometry.

PubMed

Mehder, A O; Habibullah, Y B; Gondal, M A; Baig, Umair

2016-08-01

Laser Induced Breakdown Spectroscopy (LIBS) is demonstrated for the spectral analysis of nutritional and toxic elements present in several varieties of date fruit samples available in the Saudi Arabia market. The method analyzes the optical emission of a test sample when subjected to pulsed laser ablation. In this demonstration, our primary focus is on calcium (Ca) and magnesium (Mg), as nutritional elements, and on chromium (Cr), as a toxic element. The local thermodynamic equilibrium (LTE) condition was confirmed prior to the elemental characterization of date samples to ensure accuracy of the LIBS analysis. This was achieved by measuring parameters associated with the plasma, such as the electron temperature and the electron number density. These plasma parameters aid interpretation of processes such as ionization, dissociation, and excitation occurring in the plasma plume formed by ablating the date palm sample. The minimum detection limit was established from calibration curves that involved plotting the LIBS signal intensity as a function of standard date samples with known concentrations. The concentration of Ca and Mg detected in different varieties of date samples was between 187 and 515 and 35-196mgL(-1) respectively, while Cr concentration measured between 1.72 and 7.76mgL(-1). In order to optimize our LIBS system, we have studied how the LIBS signal intensity depends on the incident laser energy and the delay time. In order to validate our LIBS analysis results, standard techniques such as inductively coupled plasma mass spectrometry (ICP-MS) were also applied on an identical (duplicate) date samples as those used for the LIBS analysis. The LIBS results exhibit remarkable agreement with those obtained from the ICP-MS analysis. In addition, the finger print wavelengths of other elements present in date samples were also identified and are reported here, which has not been previously reported, to the best of our knowledge. Copyright © 2016 Elsevier B.V. All rights reserved.

Online immunocapture ICP-MS for the determination of the metalloprotein ceruloplasmin in human serum.

PubMed

Bernevic, Bogdan; El-Khatib, Ahmed H; Jakubowski, Norbert; Weller, Michael G

2018-04-02

The human copper-protein ceruloplasmin (Cp) is the major copper-containing protein in the human body. The accurate determination of Cp is mandatory for the reliable diagnosis of several diseases. However, the analysis of Cp has proven to be difficult. The aim of our work was a proof of concept for the determination of a metalloprotein-based on online immunocapture ICP-MS. The immuno-affinity step is responsible for the enrichment and isolation of the analyte from serum, whereas the compound-independent quantitation with ICP-MS delivers the sensitivity, precision, and large dynamic range. Off-line ELISA (enzyme-linked immunosorbent assay) was used in parallel to confirm the elution profile of the analyte with a structure-selective method. The total protein elution was observed with the 32 S mass trace. The ICP-MS signals were normalized on a 59 Co signal. The human copper-protein Cp could be selectively determined. This was shown with pure Cp and with a sample of human serum. The good correlation with off-line ELISA shows that Cp could be captured and eluted selectively from the anti-Cp affinity column and subsequently determined by the copper signal of ICP-MS.

Application of CE-ICP-MS and CE-ESI-MS/MS for identification of Zn-binding ligands in Goji berries extracts.

PubMed

Ruzik, Lena; Kwiatkowski, Piotr

2018-06-01

The identification of groups of ligands binding metals is a crucial issue for the better understanding of their bioaccessibility. In the current study, we have intended an approach for identification of Zn-binding ligands based on using capillary electrophoresis combined with inductively coupled plasma mass spectrometry (CE-ICP-MS) and tandem electrospray ionization mass spectrometry (CE-ESI-MS/MS). The approach, which featured the use of the coupling of capillary electrophoresis with inductively coupled plasma mass spectrometry allows to separate and observe zinc ions present in complexes with respect to their size and charge and to identify nine compounds with zinc isotopic profile. CE-ICP-MS provides us with information about presence of zinc species and elemental information about zinc distribution. CE-ESI-MS/MS provide us with information about the most favorable Zn binding ligands: amino acids, flavonols, stilbenoids, fenolic acids and carotenoids. The presented work is the continuation of previous studies based on using LC-ESI-MS/MS, though, now we presented a new solutions with the possibility of changing detectors without changing the separation techniques, what is important without re-optimizing the method. The new presented method allows to identify the zinc-binding ligands in shorter time. Copyright © 2018 Elsevier B.V. All rights reserved.

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

PubMed Central

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

2015-01-01

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

Determination of mercury in hair: Comparison between gold amalgamation-atomic absorption spectrometry and mass spectrometry.

PubMed

Domanico, Francesco; Forte, Giovanni; Majorani, Costanza; Senofonte, Oreste; Petrucci, Francesco; Pezzi, Vincenzo; Alimonti, Alessandro

2017-09-01

Mercury is a heavy metal that causes serious health problems in exposed subjects. The most toxic form, i.e., methylmercury (MeHg), is mostly excreted through human hair. Numerous analytical methods are available for total Hg analysis in human hair, including cold vapour atomic fluorescence spectrometry (CV-AFS), inductively coupled plasma mass spectrometry (ICP-MS) and thermal decomposition amalgamation atomic absorption spectrometry (TDA-AAS). The aim of the study was to compare the TDA-AAS with the ICP-MS in the Hg quantification in human hair. After the washing procedure to minimize the external contamination, from each hair sample two aliquots were taken; the first was used for direct analysis of Hg by TDA-AAS and the second was digested for Hg determination by the ICP-MS. Results indicated that the two data sets were fully comparable (median; TDA-AAS, 475ngg -1 ; ICP-MS, 437ngg -1 ) and were not statistically different (Mann-Whitney test; p=0.44). The two techniques presented results with a good coefficient of correlation (r=0.94) despite different operative ranges and method limits. Both techniques satisfied internal performance requirements and the parameters for method validation resulting sensitive, precise and reliable. Finally, the use of the TDA-AAS can be considered instead of the ICP-MS in hair analysis in order to reduce sample manipulation with minor risk of contamination, less time consuming due to the absence of the digestion step and cheaper analyses. Copyright © 2016 Elsevier GmbH. All rights reserved.

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

USGS Publications Warehouse

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

2008-01-01

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

Developments in ICP-MS: electrochemically modulated liquid chromatography for the clean-up of ICP-MS blanks and reduction of matrix effects by flow injection ICP-MS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gross, Cory Thomas

2008-01-01

The focus of this dissertation is the development of techniques with which to enhance the existing abilities of inductively coupled plasma mass spectrometry (ICP-MS). ICP-MS is a powerful technique for trace metal analysis in samples of many types, but like any technique it has certain strengths and weaknesses. Attempts are made to improve upon those strengths and to overcome certain weaknesses.

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

PubMed

Boulyga, Sergei F; Prohaska, Thomas

2008-01-01

This paper presents the application of a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS)--a Nu Plasma HR--equipped with three ion-counting multipliers and coupled to a laser ablation system (LA) for the rapid and sensitive determination of the 235U/238U, 236U/238U, 145Nd/143Nd, 146Nd/143Nd, 101Ru/(99Ru+99Tc) and 102Ru/(99Ru+99Tc) isotope ratios in microsamples collected in the vicinity of Chernobyl. Microsamples with dimensions ranging from a hundred mum to about 1 mm and with surface alpha activities of 3-38 mBq were first identified using nuclear track radiography. U, Nd and Ru isotope systems were then measured sequentially for the same microsample by LA-MC-ICP-MS. The application of a zoom ion optic for aligning the ion beams into the ion counters allows fast switching between different isotope systems, which enables all of the abovementioned isotope ratios to be measured for the same microsample within a total analysis time of 15-20 min (excluding MC-ICP-MS optimization and calibration). The 101Ru/(99Ru+99Tc) and 102Ru/(99Ru+99Tc) isotope ratios were measured for four microsamples and were found to be significantly lower than the natural ratios, indicating that the microsamples were contaminated with the corresponding fission products (Ru and Tc). A slight depletion in 146Nd of about 3-5% was observed in the contaminated samples, but the Nd isotopic ratios measured in the contaminated samples coincided with natural isotopic composition within the measurement uncertainty, as most of the Nd in the analyzed samples originates from the natural soil load of this element. The 235U/238U and 236U/238U isotope ratios were the most sensitive indicators of irradiated uranium. The present work yielded a significant variation in uranium isotope ratios in microsamples, in contrast with previously published results from the bulk analysis of contaminated samples originating from the vicinity of Chernobyl. Thus, the 235U/238U ratios measured in ten microsamples varied in the range from 0.0073 (corresponding to the natural uranium isotopic composition) to 0.023 (corresponding to initial 235U enrichment in reactor fuel). An inverse correlation was observed between the 236U/238U and 235U/238U isotope ratios, except in the case of one sample with natural uranium. The heterogeneity of the uranium isotope composition is attributed to the different burn-up grades of uranium in the fuel rods from which the microsamples originated.

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

PubMed

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

2015-01-01

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

Separation techniques for the clean-up of radioactive mixed waste for ICP-AES/ICP-MS analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swafford, A.M.; Keller, J.M.

1993-03-17

Two separation techniques were investigated for the clean-up of typical radioactive mixed waste samples requiring elemental analysis by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) or Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). These measurements frequently involve regulatory or compliance criteria which include the determination of elements on the EPA Target Analyte List (TAL). These samples usually consist of both an aqueous phase and a solid phase which is mostly an inorganic sludge. Frequently, samples taken from the waste tanks contain high levels of uranium and thorium which can cause spectral interferences in ICP-AES or ICP-MS analysis. The removal of these interferences ismore » necessary to determine the presence of the EPA TAL elements in the sample. Two clean-up methods were studied on simulated aqueous waste samples containing the EPA TAL elements. The first method studied was a classical procedure based upon liquid-liquid extraction using tri-n- octylphosphine oxide (TOPO) dissolved in cyclohexane. The second method investigated was based on more recently developed techniques using extraction chromatography; specifically the use of a commercially available Eichrom TRU[center dot]Spec[trademark] column. Literature on these two methods indicates the efficient removal of uranium and thorium from properly prepared samples and provides considerable qualitative information on the extraction behavior of many other elements. However, there is a lack of quantitative data on the extraction behavior of elements on the EPA Target Analyte List. Experimental studies on these two methods consisted of determining whether any of the analytes were extracted by these methods and the recoveries obtained. Both methods produced similar results; the EPA target analytes were only slightly or not extracted. Advantages and disadvantages of each method were evaluated and found to be comparable.« less

Integrated approaches for reducing sample size for measurements of trace elemental impurities in plutonium by ICP-OES and ICP-MS

DOE PAGES

Xu, Ning; Chamberlin, Rebecca M.; Thompson, Pam; ...

2017-10-07

This study has demonstrated that bulk plutonium chemical analysis can be performed at small scales (\\50 mg material) through three case studies. Analytical methods were developed for ICP-OES and ICP-MS instruments to measure trace impurities and gallium content in plutonium metals with comparable or improved detection limits, measurement accuracy and precision. In two case studies, the sample size has been reduced by 109, and in the third case study, by as much as 50009, so that the plutonium chemical analysis can be performed in a facility rated for lower-hazard and lower-security operations.

Integrated approaches for reducing sample size for measurements of trace elemental impurities in plutonium by ICP-OES and ICP-MS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Ning; Chamberlin, Rebecca M.; Thompson, Pam

This study has demonstrated that bulk plutonium chemical analysis can be performed at small scales (\\50 mg material) through three case studies. Analytical methods were developed for ICP-OES and ICP-MS instruments to measure trace impurities and gallium content in plutonium metals with comparable or improved detection limits, measurement accuracy and precision. In two case studies, the sample size has been reduced by 109, and in the third case study, by as much as 50009, so that the plutonium chemical analysis can be performed in a facility rated for lower-hazard and lower-security operations.

Environmental applications of single collector high resolution ICP-MS.

PubMed

Krachler, Michael

2007-08-01

The number of environmental applications of single collector high resolution ICP-MS (HR-ICP-MS) has increased rapidly in recent years. There are many factors that contribute to make HR-ICP-MS a very powerful tool in environmental analysis. They include the extremely low detection limits achievable, tremendously high sensitivity, the ability to separate ICP-MS signals of the analyte from spectral interferences, enabling the reliable determination of many trace elements, and the reasonable precision of isotope ratio measurements. These assets are improved even further using high efficiency sample introduction systems. Therefore, external factors such as the stability of laboratory blanks are frequently the limiting factor in HR-ICP-MS analysis rather than the detection power. This review aims to highlight the most recent applications of HR-ICP-MS in this sector, focusing on matrices and applications where the superior capabilities of the instrumental technique are most useful and often ultimately required.

A fast and feasible method for Br and I determination in whole egg powder and its fractions by ICP-MS.

PubMed

Toralles, Isis Gonçalves; Coelho, Gilberto Silva; Costa, Vanize Cadeira; Cruz, Sandra Meinen; Flores, Erico Marlon Moraes; Mesko, Marcia Foster

2017-04-15

A method for Br and I determination in whole egg powder and its fractions (egg white and yolk) was developed by combining microwave-induced combustion (MIC) and inductively coupled plasma mass spectrometry (ICP-MS). Using the MIC method, 350mg of whole egg powder and its fractions were efficiently digested using 50mmolL -1 NH 4 OH as an absorbing solution. The limits of detection for Br and I using the MIC method followed by ICP-MS determination were 0.039 and 0.015μgg -1 , respectively. Using the proposed method, agreements with the reference values between 97 and 104% for Br and I were obtained by analysis of reference material NIST 8435. Finally, it was possible to observe that Br concentration (4.59-5.29μgg -1 ) was higher than I (0.150-2.28μgg -1 ) for all the evaluated samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

Evaluation of Hydrodynamic Chromatography Coupled with UV-Visible, Fluorescence and Inductively Coupled Plasma Mass Spectrometry Detectors for Sizing and Quantifying Colloids in Environmental Media

PubMed Central

Philippe, Allan; Schaumann, Gabriele E.

2014-01-01

In this study, we evaluated hydrodynamic chromatography (HDC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) for the analysis of nanoparticles in environmental samples. Using two commercially available columns (Polymer Labs-PDSA type 1 and 2), a set of well characterised calibrants and a new external time marking method, we showed that flow rate and eluent composition have few influence on the size resolution and, therefore, can be adapted to the sample particularity. Monitoring the agglomeration of polystyrene nanoparticles over time succeeded without observable disagglomeration suggesting that even weak agglomerates can be measured using HDC. Simultaneous determination of gold colloid concentration and size using ICP-MS detection was validated for elemental concentrations in the ppb range. HDC-ICP-MS was successfully applied to samples containing a high organic and ionic background. Indeed, online combination of UV-visible, fluorescence and ICP-MS detectors allowed distinguishing between organic molecules and inorganic colloids during the analysis of Ag nanoparticles in synthetic surface waters and TiO2 and ZnO nanoparticles in commercial sunscreens. Taken together, our results demonstrate that HDC-ICP-MS is a flexible, sensitive and reliable method to measure the size and the concentration of inorganic colloids in complex media and suggest that there may be a promising future for the application of HDC in environmental science. Nonetheless the rigorous measurements of agglomerates and of matrices containing natural colloids still need to be studied in detail. PMID:24587393

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.

Evaluation of hydrodynamic chromatography coupled with UV-visible, fluorescence and inductively coupled plasma mass spectrometry detectors for sizing and quantifying colloids in environmental media.

PubMed

Philippe, Allan; Schaumann, Gabriele E

2014-01-01

In this study, we evaluated hydrodynamic chromatography (HDC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) for the analysis of nanoparticles in environmental samples. Using two commercially available columns (Polymer Labs-PDSA type 1 and 2), a set of well characterised calibrants and a new external time marking method, we showed that flow rate and eluent composition have few influence on the size resolution and, therefore, can be adapted to the sample particularity. Monitoring the agglomeration of polystyrene nanoparticles over time succeeded without observable disagglomeration suggesting that even weak agglomerates can be measured using HDC. Simultaneous determination of gold colloid concentration and size using ICP-MS detection was validated for elemental concentrations in the ppb range. HDC-ICP-MS was successfully applied to samples containing a high organic and ionic background. Indeed, online combination of UV-visible, fluorescence and ICP-MS detectors allowed distinguishing between organic molecules and inorganic colloids during the analysis of Ag nanoparticles in synthetic surface waters and TiO₂ and ZnO nanoparticles in commercial sunscreens. Taken together, our results demonstrate that HDC-ICP-MS is a flexible, sensitive and reliable method to measure the size and the concentration of inorganic colloids in complex media and suggest that there may be a promising future for the application of HDC in environmental science. Nonetheless the rigorous measurements of agglomerates and of matrices containing natural colloids still need to be studied in detail.

Direct determination of cadmium in foods by solid sampling electrothermal vaporization inductively coupled plasma mass spectrometry using a tungsten coil trap

NASA Astrophysics Data System (ADS)

Zhang, Ying; Mao, Xuefei; Liu, Jixin; Wang, Min; Qian, Yongzhong; Gao, Chengling; Qi, Yuehan

2016-04-01

In this work, a solid sampling device consisting of a tungsten coil trap, porous carbon vaporizer and on-line ashing furnace of a Ni-Cr coil was interfaced with inductively coupled plasma mass spectrometry (ICP-MS). A modified double gas circuit system was employed that was composed of carrier and supplemental gas lines controlled by separate gas mass flow controllers. For Cd determination in food samples using the assembled solid sampling ICP-MS, the optimal ashing and vaporization conditions, flow rate of the argon-hydrogen (Ar/H2) (v:v = 24:1) carrier gas and supplemental gas, and minimum sampling mass were investigated. Under the optimized conditions, the limit of quantification was 0.5 pg and the relative standard deviation was within a 10.0% error range (n = 10). Furthermore, the mean spiked recoveries for various food samples were 99.4%-105.9% (n = 6). The Cd concentrations measured by the proposed method were all within the certified values of the reference materials or were not significantly different (P > 0.05) from those of the microwave digestion ICP-MS method, demonstrating the good accuracy and precision of the solid sampling ICP-MS method for Cd determination in food samples.

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

EPA Science Inventory

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

Speciation of aluminum in drink samples by 8-hydroxyquinoline loaded silylanization silica gel microcolumn separation with off-line ICP-MS detection.

PubMed

Chen, Jie; Huang, Chaozhang; Hu, Bin; Jiang, Zucheng

2004-11-17

A technique using a flow injection microcolumn separation coupled with ICP-MS detection has been developed for the speciation of Al in drink samples. The retention behaviors of different Al species were studied with 8-hydroxyquinoline (8-HQ) loaded silylanization silica gel as the packing material and inorganic acid (HNO3) as the elution. The results indicated that in a pH range of 5.0 to 8.0, all labile monomeric Al species were retained on the microcolumn while nonlabile monomeric Al species were directly passed through the column. Various Al species after separation were detected by ICP-MS. The detection limit of 0.2 ng mL(-1) and a relative standard deviation (RSD) of 4.2% at 10 ng mL(-1) (n = 11) were achieved, and the recoveries for the spiked samples were 95-108%. The proposed method has been applied to the analysis of Al species in tea infusions, coffee, and tap waters with satisfactory results. The results obtained by this method were compared with that obtained by the cation exchange microcolumn separation and ICP-MS detection system, and some valuable conclusions were drawn.

Fast and accurate determination of arsenobetaine in fish tissues using accelerated solvent extraction and HPLC-ICP-MS determination.

PubMed

Wahlen, Raimund

2004-04-01

A high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) method has been developed for the fast and accurate analysis of arsenobetaine (AsB) in fish samples extracted by accelerated solvent extraction. The combined extraction and analysis approach is validated using certified reference materials for AsB in fish and during a European intercomparison exercise with a blind sample. Up to six species of arsenic (As) can be separated and quantitated in the extracts within a 10-min isocratic elution. The method is optimized so as to minimize time-consuming sample preparation steps and allow for automated extraction and analysis of large sample batches. A comparison of standard addition and external calibration show no significant difference in the results obtained, which indicates that the LC-ICP-MS method is not influenced by severe matrix effects. The extraction procedure can process up to 24 samples in an automated manner, yet the robustness of the developed HPLC-ICP-MS approach is highlighted by the capability to run more than 50 injections per sequence, which equates to a total run-time of more than 12 h. The method can therefore be used to rapidly and accurately assess the proportion of nontoxic AsB in fish samples with high total As content during toxicological screening studies.

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

PubMed Central

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

2016-01-01

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

Magnetophoretic separation ICP-MS immunoassay using Cs-doped multicore magnetic nanoparticles for the determination of salmonella typhimurium.

PubMed

Jeong, Arong; Lim, H B

2018-02-01

In this work, a magnetophoretic separation ICP-MS immunoassay using newly synthesized multicore magnetic nanoparticles (MMNPs) was developed for the determination of salmonella typhimurium (typhi). The uniqueness of this method was the use of MMNPs doped with Cs for both separation and detection, which enable us to achieve fast analysis, high sensitivity, and good reliability. For demonstration, heat-killed typhi in a phosphate buffer solution was determined by ICP-MS after the MMNP-typhi reaction product was separated from unreacted MMNPs in a micropipette tip filled with 25% polyethylene glycol through magnetophoretic separation. The calibration curve obtained by plotting 133 Cs intensity vs. the number of synthetic standard, showed a coefficient of determination (R 2 ) of 0.94 with a limit of detection (LOD) of 102 cells/mL without cell culturing. Excellent recoveries, between 98-100%, were obtained from four replicates and compared with a sandwich-type ICP-MS immunoassay for further confirmation. Copyright © 2017 Elsevier B.V. All rights reserved.

Rapid and simple determination of selenium in blood serum by inductively coupled plasma-mass spectrometry (ICP-MS).

PubMed

Labat, L; Dehon, B; Lhermitte, M

2003-05-01

An inductively coupled plasma mass spectrometer (ICP-MS) with a rapid sample-preparative procedure was used for the determination of selenium in blood serum. Blood serum was prepared by dilution in an acidic solution consisting of nitric acid (1%), X-triton (0.1%) and 1-butanol (0.8%). A calibration curve was established for 1-40 microg mL(-1) (r(2)>0.99). The limit of detection was 0.5 microg mL(-1). Repeatability and intermediate precision were satisfactory with relative standard deviations (RSD) of 2.0% and 3.2%, respectively. This method was easily applied to reference materials with satisfactory accuracy. Good correlation (r(2)=0.96) was observed between ICP-MS and atomic absorption spectrometry (AAS) for the determination of (82)Se in blood serum from 23 patients. These results suggest that the sample preparative procedure coupled with ICP-MS can be used for the routine determination of (82)Se in human blood serum.

Establishment of a method for determination of arsenic species in seafood by LC-ICP-MS.

PubMed

Zmozinski, Ariane V; Llorente-Mirandes, Toni; López-Sánchez, José F; da Silva, Márcia M

2015-04-15

An analytical method for determination of arsenic species (inorganic arsenic (iAs), methylarsonic acid (MA), dimethylarsinic acid (DMA), arsenobetaine (AB), trimethylarsine oxide (TMAO) and arsenocholine (AC)) in Brazilian and Spanish seafood samples is reported. This study was focused on extraction and quantification of inorganic arsenic (iAs), the most toxic form. Arsenic speciation was carried out via LC with both anionic and cationic exchange with ICP-MS detection (LC-ICP-MS). The detection limits (LODs), quantification limits (LOQs), precision and accuracy for arsenic species were established. The proposed method was evaluated using eight reference materials (RMs). Arsenobetaine was the main species found in all samples. The total and iAs concentration in 22 seafood samples and RMs ranged between 0.27-35.2 and 0.02-0.71 mg As kg(-1), respectively. Recoveries ranging from 100% to 106% for iAs, based on spikes, were achieved. The proposed method provides reliable iAs data for future risk assessment analysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

ICP-MS multielemental determination of metals potentially released from dental implants and articular prostheses in human biological fluids.

PubMed

Sarmiento-González, Alejandro; Marchante-Gayón, Juan Manuel; Tejerina-Lobo, José María; Paz-Jiménez, José; Sanz-Medel, Alfredo

2005-06-01

A sector field high-resolution (HR)-ICP-MS and an octapole reaction system (ORS)-ICP-MS have been compared for the simultaneous determination of traces of metals (Ti, V, Cr, Co, Ni, and Mo) released from dental implants and articular prostheses in human biological fluids. Optimum sample treatments were evaluated to minimize matrix effects in urine and whole blood. Urine samples were diluted tenfold with ultrapure water, whereas whole blood samples were digested with high-purity nitric acid and hydrogen peroxide and finally diluted tenfold with ultrapure water. In both matrices, internal standardization (Ga and Y) was employed to avoid potential matrix interferences and ICP-MS signal drift. Spectral interferences arising from the plasma gases or the major components of urine and whole blood were identified by (HR)-ICP-MS at 3,000 resolving power. The capabilities of (HR)-ICP-MS and (ORS)-ICP-MS for the removal of such spectral interferences were evaluated and compared. Results indicate that polyatomic interferences, which hamper the determination of such metallic elements in these biological samples, could be overcome by using a resolving power of 3,000. Using (ORS)-ICP-MS, all those elements could be quantified except Ti and V (due to the polyatomic ions 31P16O and 35Cl16O, respectively). The accuracy of the proposed methodologies by (HR)- and (ORS)-ICP-MS was checked against two reference materials. Good agreement between the given values and the concentrations obtained for all the analytes under scrutiny was found except for Ti and V when analyzed by (ORS)-ICP-MS.

Electrothermal Vaporization-QQQ-ICP-MS for Determination of Chromium in Mainstream Cigarette Smoke Particulate.

PubMed

Fresquez, Mark R; Gonzalez-Jimenez, Nathalie; Gray, Naudia; Valentin-Blasini, Liza; Watson, Clifford H; Pappas, R Steven

2017-05-01

Chromium is transported in mainstream tobacco smoke at very low concentrations. However, when chromium is deposited too deeply in the lungs for mucociliary clearance, or is in a particle that is too large to pass directly through tissues, it bioaccumulates in the lungs of smokers. It is important to determine the concentrations of chromium that are transported in mainstream smoke. Several reliable studies have resulted in reports of chromium concentrations in smoke particulate that were below limits of detection (LODs) for the instruments and methods employed. In this study, electrothermal vaporization-triple quad-inductively coupled plasma-mass spectrometry (ETV-QQQ-ICP-MS) was chosen for determination of chromium concentrations in mainstream smoke because of the high sensitivity of ETV combined with QQQ-ICP-MS. The smoke from five reference, quality control, and commercial cigarettes was analyzed using ETV-QQQ-ICP-MS with isotope dilution for quantitative determination of chromium. The method LOD was sufficiently low that chromium concentrations in mainstream smoke could indeed be determined. The chromium concentrations in the smoke particulate were between 0.60 and 1.03 ng/cigarette. The range of chromium concentrations was at or below previously reported LODs. Determination of the oxidation state of the chromium transported in mainstream smoke would also be important, in consideration of the fact that both chromium(III) and chromium(VI) oxidation states cause inhalation toxicity, but chromium(VI) is also a carcinogen. It was possible to separate the oxidation states using ETV-QQQ-ICP-MS. However, determination of individual species at the levels found in mainstream smoke particulate matter was not possible with the present method. Published by Oxford University Press 2017. This work is written by (a) US Government employee(s) and is in the public domain in the US.

Electrothermal Vaporization-QQQ-ICP-MS for Determination of Chromium in Mainstream Cigarette Smoke Particulate

PubMed Central

Fresquez, Mark R.; Gonzalez-Jimenez, Nathalie; Gray, Naudia; Valentin-Blasini, Liza; Watson, Clifford H.; Pappas, R. Steven

2017-01-01

Chromium is transported in mainstream tobacco smoke at very low concentrations. However, when chromium is deposited too deeply in the lungs for mucociliary clearance, or is in a particle that is too large to pass directly through tissues, it bioaccumulates in the lungs of smokers. It is important to determine the concentrations of chromium that are transported in mainstream smoke. Several reliable studies have resulted in reports of chromium concentrations in smoke particulate that were below limits of detection for the instruments and methods employed. In this study, electrothermal vaporization-triple quad-inductively coupled plasma-mass spectrometry (ETV-QQQ-ICP-MS) was chosen for determination of chromium concentrations in mainstream smoke because of the high sensitivity of ETV combined with QQQ-ICP-MS. The smoke from five reference, quality control, and commercial cigarettes was analyzed using ETV-QQQ-ICP-MS with isotope dilution for quantitative determination of chromium. The method limit of detection (LOD) was sufficiently low that chromium concentrations in mainstream smoke could indeed be determined. The chromium concentrations in the smoke particulate were between 0.60 and 1.03 ng/cigarette. The range of chromium concentrations was at or below previously reported LODs. Determination of the oxidation state of the chromium transported in mainstream smoke would also be important, in consideration of the fact that both chromium(III) and chromium(VI) oxidation states cause inhalation toxicity, but chromium(VI) is also a carcinogen. It was possible to separate the oxidation states using ETV-QQQ-ICP-MS. However, determination of individual species at the levels found in mainstream smoke particulate matter was not possible with the present method. PMID:28164228

Species and life-history affects the utility of otolith chemical composition to determine natal stream-of-origin in Pacific salmon

USGS Publications Warehouse

Zimmerman, Christian E.; Swanson, Heidi K.; Volk, Eric C.; Kent, Adam J.R.

2013-01-01

To test the utility of otolith chemical composition as a tool for determining the natal stream of origin for salmon, we examined water chemistry and otoliths of juvenile and adult Chum Salmon Oncorhynchus keta and Coho Salmon O. kisutch from three watersheds (five rivers) in the Norton Sound region of Alaska. The two species are characterized by different life histories: Coho Salmon rear in freshwater for up to 3 years, whereas Chum Salmon emigrate from freshwater shortly after emergence. We used laser ablation (LA) inductively coupled plasma (ICP) mass spectrometry (MS) to quantify element: Ca ratios for Mg, Mn, Zn, Sr, and Ba, and we used multicollector LA-ICP-MS to determine 87Sr:86Sr ratios in otolith regions corresponding to the period of freshwater residence. Significant differences existed in both water and otolith elemental composition, suggesting that otolith composition could be used to discriminate the natal origin of Coho Salmon and Chum Salmon but only when 87Sr:86Sr ratios were included in the discriminant function analyses. The best discriminant model included 87Sr:86Sr ratios, and without 87Sr:86Sr ratios it was difficult to discriminate among watersheds and rivers. Classification accuracy was 80% for Coho Salmon and 68% for Chum Salmon, indicating that this method does not provide sufficient sensitivity to estimate straying rates of Pacific salmon at the scale we studied.

Determinations of rare earth element abundance and U-Pb age of zircons using multispot laser ablation-inductively coupled plasma mass spectrometry.

PubMed

Yokoyama, Takaomi D; Suzuki, Toshihiro; Kon, Yoshiaki; Hirata, Takafumi

2011-12-01

We have developed a new calibration technique for multielement determination and U-Pb dating of zircon samples using laser ablation-inductively coupled plasma mass spectrometry (ICPMS) coupled with galvanometric optics. With the galvanometric optics, laser ablation of two or more sample materials could be achieved in very short time intervals (~10 ms). The resulting sample aerosols released from different ablation pits or different solid samples were mixed and homogenized within the sample cell and then transported into the ICP ion source. Multiple spot laser ablation enables spiking of analytes or internal standard elements directly into the solid samples, and therefore the standard addition calibration method can be applied for the determination of trace elements in solid samples. In this study, we have measured the rare earth element (REE) abundances of two zircon samples (Nancy 91500 and Prešovice) based on the standard addition technique, using a direct spiking of analytes through a multispot laser ablation of the glass standard material (NIST SRM612). The resulting REE abundance data show good agreement with previously reported values within analytical uncertainties achieved in this study (10% for most elements). Our experiments demonstrated that nonspectroscopic interferences on 14 REEs could be significantly reduced by the standard addition technique employed here. Another advantage of galvanometric devices is the accumulation of sample aerosol released from multiple spots. In this study we have measured the U-Pb age of a zircon sample (LMR) using an accumulation of sample aerosols released from 10 separate ablation pits of low diameters (~8 μm). The resulting (238)U-(206)Pb age data for the LMR zircons was 369 ± 64 Ma, which is in good agreement with previously reported age data (367.6 ± 1.5 Ma). (1) The data obtained here clearly demonstrate that the multiple spot laser ablation-ICPMS technique can become a powerful approach for elemental and isotopic ratio measurements in solid materials.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 splitmore » 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. Multiple vacuum box locations may be set-up to supply several ICP-MS units with purified sample fractions such that a high sample throughput may be achieved, while still allowing for rapid measurement of short-lived actinides by alpha spectrometry.« less

Improved approach for routine monitoring of 129I activity and 129I/127I atom ratio in environmental samples using TMAH extraction and ICP-MS/MS.

PubMed

Yang, Guosheng; Tazoe, Hirofumi; Yamada, Masatoshi

2018-05-30

To reconstruct 131 I deposition and identify the source of radioiodine due to the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident, 129 I activity and 129 I/ 127 I atom ratio should be obtained by preparing and analyzing large numbers of samples economically. In this study, great efforts were made to realize mild TMAH (tetramethyl ammonium hydroxide) extraction of environmental samples at 90 °C to obtain solutions suitable for the following triple-quadrupole inductively coupled plasma-mass spectrometry (ICP-QQQ) MS/MS mode analysis. After releasing iodine from organic matter in the TMAH extraction solution via K 2 S 2 O 8 oxidation, organic matter was removed effectively by solvent extraction and back-extraction to avoid a serious matrix effect during ICP-QQQ analysis. At the same time, interfering elements, especially, Mo, Cd, and In were also removed effectively, to avoid their undesirable interferences during mass spectrometric analysis. In addition, 0.01% (NH 4 ) 2 SO 3 was selected to introduce I - into ICP-QQQ to ensure there was no memory effect and a stable signal was gotten. Subsequently, ICP-QQQ MS/MS mode was applied to further eliminate polyatomic interferences ( 127 I(H 2 and D) + , 97 MoO 2 + , 113 InO + , and 113 CdO + ) and isobaric interference from 129 Xe + . Finally, the developed method was successfully applied to measure 129 I/ 127 I atom ratios ((2.61-27.0) × 10 -7 ) and 129 I activities (3.51-11.4 mBq kg -1 ) in soil samples. The developed method allows a greater number of ordinary laboratories to participate in the field of radioiodine analysis. Copyright © 2018 Elsevier B.V. All rights reserved.

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

PubMed

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

2016-08-15

In this work a green digestion method which only used H2O2 as an oxidant and high temperature and pressure in the single reaction chamber system (SRC-UltraWave™) was applied for subsequent elemental determination by inductively coupled plasma-based techniques. Milk powder was chosen to demonstrate the feasibility and advantages of the proposed method. Samples masses up to 500mg were efficiently digested, and the determination of Ca, Fe, K, Mg and Na was performed by inductively coupled plasma optical emission spectrometry (ICP-OES), while trace elements (B, Ba, Cd, Cu, Mn, Mo, Pb, Sr and Zn) were determined by inductively coupled plasma mass spectrometry (ICP-MS). Residual carbon (RC) lower than 918mgL(-1) of C was obtained for digests which contributed to minimizing interferences in determination by ICP-OES and ICP-MS. Accuracy was evaluated using certified reference materials NIST 1549 (non-fat milk powder certified reference material) and NIST 8435 (whole milk powder reference material). The results obtained by the proposed method were in agreement with the certified reference values (t-test, 95% confidence level). In addition, no significant difference was observed between results obtained by the proposed method and conventional wet digestion using concentrated HNO3. As digestion was performed without using any kind of acid, the characteristics of final digests were in agreement with green chemistry principles when compared to digests obtained using conventional wet digestion method with concentrated HNO3. Additionally, H2O2 digests were more suitable for subsequent analysis by ICP-based techniques due to of water being the main product of organic matrix oxidation. The proposed method was suitable for quality control of major components and trace elements present in milk powder in consonance with green sample preparation. Copyright © 2016 Elsevier B.V. All rights reserved.

Screening of TiO2 and Au nanoparticles in cosmetics and determination of elemental impurities by multiple techniques (DLS, SP-ICP-MS, ICP-MS and ICP-OES).

PubMed

de la Calle, Inmaculada; Menta, Mathieu; Klein, Marlène; Séby, Fabienne

2017-08-15

Cosmetics are part of the daily life of most of the people. Thus, a complete characterization of the products we applied in our skin is necessary. In this work, an analytical investigation of a wide variety of cosmetics from the point of view of total element content and metallic nanoparticles (NPs) has been performed. Firstly, we analyzed the total element content by ICP-MS and ICP-OES after acid digestion as an assessment of the presence of metal impurities. Prohibited elements in cosmetics, according to the European Commission regulation No 1223/2009, were not detected, and only elements mentioned in the label were found (e.g. Al, Fe, Ti and Si). Secondly, a screening of the presence of NPs has been performed by Dynamic Light Scattering (DLS) and Single Particle Inductively-Coupled Plasma Mass Spectrometry (SP-ICP-MS). Two sample preparation procedures were applied. The first protocol consisted in the preparation of suspensions in 0.1% w/v SDS and the second based on defatting with hexane followed by resuspension in water. DLS was employed as a routine method for a fast analysis of NPs, but this technique showed limitations due to the lack of specificity. SP-ICP-MS analyses were then performed, first as a screening technique to evaluate the presence of TiO 2 and Au NPs in cosmetics suspensions prepared in SDS; and second, when a positive answer was obtained about the presence of NPs from the screening, SP-ICP-MS was used for particle size determination. Results showed that only TiO 2 NPs were present in two sunscreens, one anti-wrinkle day cream, one lip balm protector labeled as 'nano' and in one brand of toothpaste not labeled as 'nano'. Sizes obtained for both sample preparations were compared and ranged from 30 to 120nm in most of the samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Two-dimensional on-line detection of brominated and iodinated volatile organic compounds by ECD and ICP-MS after GC separation.

PubMed

Schwarz, A; Heumann, K G

2002-09-01

Inductively coupled plasma-mass spectrometry (ICP-MS) was coupled to a gas chromatographic (GC) system with electron capture detector (ECD), which enables relatively easy characterization and quantification of brominated and iodinated (halogenated) volatile organic compounds (HVOCs) in aquatic and air samples. The GC-ECD system is connected in series with an ICP-MS by a directly heated transfer line and an outlet port-hole for elimination of the ECD make-up gas during ignition of the plasma. The hyphenated GC-ECD/ICP-MS system provides high selectivity and sensitivity for monitoring individual HVOCs under fast chromatographic conditions. The ECD is most sensitive for the detection of chlorinated and brominated but the ICP-MS for iodinated compounds. The greatest advantage of the use of an ICP-MS is its element-specific detection, which allows clear identification of compounds in most cases. The absolute detection limits for ICP-MS are 0.5 pg for iodinated, 10 pg for brominated, and 50 pg for chlorinated HVOCs with the additional advantage that calibration is almost independent on different compounds of the same halogen. In contrast to that detection limits for ECD vary for the different halogenated compounds and lie in the range of 0.03-11 pg. The two-dimensional GC-ECD/ICP-MS instrumentation is compared with electron impact mass spectrometry (EI-MS) and microwave induced plasma atomic emission detection (MIP-AED). Even if EI-MS has additional power in identifying unknown peaks by its scan mode, the detection limits are much higher compared with GC-ECD/ICP-MS, whereas the selective ion monitoring mode (SIM) reaches similar detection limits. The MIP-AED detection limits are at the same level as EI-MS in the scan mode.

Evaluating the cause(s) of Ti, Ta, and Nb (TITAN) enrichment in ocean island basalts using LA-ICP-MS

NASA Astrophysics Data System (ADS)

Lyakov, J.; Durkin, K.; Hirsch, L.; Peters, B.; Hattingh, R.; Day, J. M.

2017-12-01

Titanium, Ta, and Nb (TITAN) enrichments in some ocean island basalt (OIB) lavas have been attributed to mantle source, or to partial melting and fractional crystallization Iprocesses. TITAN anomalies in the mantle sources of OIB would imply these trace elements can be used to track mantle heterogeneity in a manner similar to some isotopic tracers (e.g., He, Os, W), whereas a petrogenetic process to account for TITAN anomalies would be more prosaic. To further evaluate this issue, we have performed laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) of phenocryst phases and matrix on petrographically well-characterized polished-sections of OIB samples. These samples come from five ocean island archipelagos (Canary Islands, the Azores, Samoa, Tubuai'i, Réunion), and are used to assess the citing of Ti, Ta, Nb and associated trace-elements within bulk-rocks. We find poorly-defined but broadly positive correlations between olivine and clinopyroxene modal abundance and Ta/Ta*, Nb/Nb*, but no correlation with Ti/Ti* (where, for example, Ti/Ti* is the primitive mantle normalized ratio, written as: Ti/√[Sm × Tb]). Abundances of olivine and clinopyroxene with samples spanned a wide-range, from 0-70 modal %. We determined trace-element abundances by LA-ICP-MS in a sub-set of samples for major (olivine, clinopyroxene) and minor (e.g., magnetite) phenocryst phases, and for the typically vitrophyric to partly crystallized matrices of samples. Modal reconstruction relative to the bulk rock are broadly similar, although the Ta/Ta*, Nb/Nb* and, especially Ti/Ti* anomalies cannot always be reproduced, especially if Fe-Ti oxide phases were not analyzed due to their limited presence within polished sections. LA-ICP-MS analyses reveal that, while TITAN anomalies are dominantly preserved in the matrix and oxide phases, the role of fractional crystallization of olivine and clinopyroxene is a controlling factor in the magnitude of TITAN anomaly generated. Our results support suggestions that Ti, Ta and Nb are affected by partial melting, assimilation and fractional crystallization processes during magma evolution, generating more prominent TITAN anomalies in volcanic samples than their mantle sources.

Investigating the Microscopic Location of Trace Elements in High-Alpine Glacier Ice

NASA Astrophysics Data System (ADS)

Avak, Sven Erik; Birrer, Mario; Laurent, Oscar; Guillong, Marcel; Wälle, Markus; Jenk, Theo Manuel; Bartels-Rausch, Thorsten; Schwikowski, Margit; Eichler, Anja

2017-04-01

Past changes in atmospheric pollution can be reconstructed from high-alpine ice core trace element records (Schwikowski et al., 2004). Percolation of meltwater alters the information originally stored in these environmental archives. Eichler et al. (2001) suggested that the preservation of major ions with respect to meltwater percolation depends on their location in the crystal ice lattice, i.e. grain boundaries versus grain interiors. Other studies have also focused on the effect of meltwater on organic pollutant concentrations as well as on stable isotope profiles in ice cores, whereas no information exists about trace elements. Here, we investigate for the first time the effect of the microscopic location of anthropogenic, dust and volcanic related trace elements on the behavior during meltwater percolation by using two different approaches. On the one hand we assess the microscopic location of trace elements indirectly by analyzing trace element concentrations in a high-alpine ice core, which has been shown to be affected by an inflow of meltwater, using discrete inductively coupled plasma mass spectrometry (ICP-MS). Impurities located at grain boundaries are prone to be removed by meltwater and tend to be depleted in the affected section of the record whereas those incorporated into the ice interior are preserved and not disturbed in the record. In the second approach we work towards a direct quantification of differences in concentrations of trace elements between ice grain boundaries and grain interiors in samples both from unaffected and affected sections of this ice core. Therefore we use cryocell laser ablation (LA) ICP-MS, which is the method of choice for the direct in situ chemical analysis of trace elements at a sub-millimeter resolution in glacier ice (Reinhardt et al., 2001, Della Lunga et al., 2014, Sneed et al., 2015). We will present first results of both approaches with regard to the evaluation of the potential of trace elements as environmental proxies in glaciers partially affected by melting. References Della Lunga, D., Müller, W., Rasmussen, S. O. & Svensson, A. 2014: Location of cation impurities in NGRIP deep ice revealed by cryo-cell UV-laser-ablation ICPMS, Journal of Glaciology, 60, 970-988. Eichler, A., Schwikowski, M., Gäggeler, H. W. 2001: Meltwater-induced relocation of chemical species in Alpine firn, Tellus B, 53, 192-203. Reinhardt, H., Kriews, M., Miller, H., Schrems, O., Lüdke, C., Hoffmann, E. & Skole, J. 2001: Laser ablation inductively coupled plasma mass spectrometry: a new tool for trace element analysis in ice cores, Fresenius' Journal of Analytical Chemistry, 370, 629-636. Schwikowski, M., Barbante, C., Doering, T., Gäggeler, H. W., Boutron, C., Schotterer, U., Tobler, L., van de Velde, K., Ferrari, C., Cozzi, G., Rosman, K., Cescon, P. 2004: Post-17th-Century Changes of European Lead Emissions Recorded in High-Altitude Alpine Snow and Ice, Environmental Science & Technology, 38, 957-964. Sneed, S. B., Mayewski, P. A., Sayre, W. G., Handley, M. J., Kurbatov, A. V., Taylor, K. C., Bohleber, P., Wagenbach, D., Erhardt, T. & Spaulding, N. E. 2015: New LA-ICP-MS cryocell and calibration technique for sub-millimeter analysis of ice cores, Journal of Glaciology, 61, 233-242.

Inductively coupled plasma mass spectrometry and electrospray mass spectrometry for speciation analysis: applications and instrumentation

NASA Astrophysics Data System (ADS)

Rosen, Amy L.; Hieftje, Gary M.

2004-02-01

To gain an understanding of the function, toxicity and distribution of trace elements, it is necessary to determine not only the presence and concentration of the elements of interest, but also their speciation, by identifying and characterizing the compounds within which each is present. For sensitive detection of compounds containing elements of interest, inductively coupled plasma mass spectrometry (ICP-MS) is a popular method, and for identification of compounds via determination of molecular weight, electrospray ionization mass spectrometry (ESI-MS) is gaining increasing use. ICP-MS and ESI-MS, usually coupled to a separation technique such as chromatography or capillary electrophoresis, have already been applied to a large number of research problems in such diverse fields as environmental chemistry, nutritional science, and bioinorganic chemistry, but a great deal of work remains to be completed. Current areas of research to which ICP-MS and ESI-MS have been applied are discussed, and the existing instrumentation used to solve speciation problems is described.

Characterisation of mineral deposition systems associated with rock art in the Kimberley region of northwest Australia.

PubMed

Green, Helen; Gleadow, Andrew; Finch, Damien

2017-10-01

This data article contains mineralogical and chemical data from mineral accretions sampled from rock art shelters in the Kimberley region of north west Australia. The accretions were collected both on and off pigment and engraved rock art of varying styles observed in the Kimberley with an aim of providing a thorough understanding of the formation and preservation of such materials in the context of dating [1]. This contribution includes processed powder X-ray Diffraction data, Scanning Electron Microscopy energy dispersive spectroscopy data, and Laser Ablation ICP-MS trace element mapping data.

Accurate determination of sulfur in gasoline and related fuel samples using isotope dilution ICP-MS with direct sample injection and microwave-assisted digestion.

PubMed

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

2004-09-01

Inductively coupled plasma isotope-dilution mass spectrometry (ICP-IDMS) with direct injection of isotope-diluted samples into the plasma, using a direct injection high-efficiency nebulizer (DIHEN), was applied for accurate sulfur determinations in sulfur-free premium gasoline, gas oil, diesel fuel, and heating oil. For direct injection a micro-emulsion consisting of the corresponding organic sample and an aqueous 34S-enriched spike solution with additions of tetrahydronaphthalene and Triton X-100, was prepared. The ICP-MS parameters were optimized with respect to high sulfur ion intensities, low mass-bias values, and high precision of 32S/34S ratio measurements. For validation of the DIHEN-ICP-IDMS method two certified gas oil reference materials (BCR 107 and BCR 672) were analyzed. For comparison a wet-chemical ICP-IDMS method was applied with microwave-assisted digestion using decomposition of samples in a closed quartz vessel inserted into a normal microwave system. The results from both ICP-IDMS methods agree well with the certified values of the reference materials and also with each other for analyses of other samples. However, the standard deviation of DIHEN-ICP-IDMS was about a factor of two higher (5-6% RSD at concentration levels above 100 mircog g(-1)) compared with those of wet-chemical ICP-IDMS, mainly due to inhomogeneities of the micro-emulsion, which causes additional plasma instabilities. Detection limits of 4 and 18 microg g(-1) were obtained for ICP-IDMS in connection with microwave-assisted digestion and DIHEN-ICP-IDMS, respectively, with a sulfur background of the used Milli-Q water as the main limiting factor for both methods.

Determination of traces of 237Np in environmental samples by ICP-MS after separation using TOA extraction chromatography.

PubMed

Ji, Y Q; Li, J Y; Luo, S G; Wu, T; Liu, J L

2001-09-01

A simple, rapid, cost-efficient, and robust method for separation of 237Np with an extraction chromatographic column (TOA: tri-n-octylamine on Teflon powder) is outlined in detail and further improved for direct ICP-MS analysis. The column efficiently retained 237Np in 2 mol L(-1) HNO3 medium and all of the 237Np was easily eluted with 0.02 mol L(-1) oxalic acid in 0.16 mol L(-1) HNO3 at 95 degrees C. The separated solutions were free from most matrix elements and were aspirated into the ICP-MS directly. The decontamination factor for 238U is more than 10(4). The instrumental detection limit for 237Np was 0.46 pg mL(-1), which corresponds to 1.2 x 10(-5) Bq mL(-1). The method is more rapid than traditional radiometric techniques. It is also considered to be more suitable for environmental monitoring than existing methods based on TOA.

Determination of uranium in tap water by ICP-MS.

PubMed

El Himri, M; Pastor, A; de la Guardia, M

2000-05-01

A fast and accurate procedure has been developed for the determination of uranium at microg L(-1) level in tap and mineral water. The method is based on the direct introduction of samples, without any chemical pre-treatment, into an inductively coupled plasma mass spectrometer (ICP-MS). Uranium was determined at the mass number 238 using Rh as internal standard. The method provides a limit of detection of 2 ng L(-1) and a good repeatability with relative standard deviation values (RSD) about 3% for five independent analyses of samples containing 73 microg L(-1) of uranium. Recovery percentage values found for the determination of uranium in spiked natural samples varied between 91% and 106%. Results obtained are comparable with those found by radiochemical methods for natural samples and of the same order for the certified content of a reference material, thus indicating the accuracy of the ICP-MS procedure without the need of using isotope dilution. A series of mineral and tap waters from different parts of Spain and Morocco were analysed.

Size exclusion chromatography with online ICP-MS enables molecular weight fractionation of dissolved phosphorus species in water samples.

PubMed

Venkatesan, Arjun K; Gan, Wenhui; Ashani, Harsh; Herckes, Pierre; Westerhoff, Paul

2018-04-15

Phosphorus (P) is an important and often limiting element in terrestrial and aquatic ecosystem. A lack of understanding of its distribution and structures in the environment limits the design of effective P mitigation and recovery approaches. Here we developed a robust method employing size exclusion chromatography (SEC) coupled to an ICP-MS to determine the molecular weight (MW) distribution of P in environmental samples. The most abundant fraction of P varied widely in different environmental samples: (i) orthophosphate was the dominant fraction (93-100%) in one lake, two aerosols and DOC isolate samples, (ii) species of 400-600 Da range were abundant (74-100%) in two surface waters, and (iii) species of 150-350 Da range were abundant in wastewater effluents. SEC-DOC of the aqueous samples using a similar SEC column showed overlapping peaks for the 400-600 Da species in two surface waters, and for >20 kDa species in the effluents, suggesting that these fractions are likely associated with organic matter. The MW resolution and performance of SEC-ICP-MS agreed well with the time integrated results obtained using conventional ultrafiltration method. Results show that SEC in combination with ICP-MS and DOC has the potential to be a powerful and easy-to-use method in identifying unknown fractions of P in the environment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Analysis of PBDEs in soil, dust, spiked lake water, and human serum samples by hollow fiber-liquid phase microextraction combined with GC-ICP-MS.

PubMed

Xiao, Qin; Hu, Bin; Duan, Jiankun; He, Man; Zu, Wanqing

2007-10-01

A novel method for the analysis of four polybrominated diphenyl ethers (PBDEs) in environmental and human serum samples based on hollow fiber-liquid phase microextraction (HF-LPME) followed by gas chromatography-inductively coupled plasma mass spectrometric (GC-ICP-MS) detection has been developed. The organic solvent in the porous hollow fiber was first dipped into the sample for extraction at a given time, and the retracted organic phase was introduced into the GC-ICP-MS for analysis. The addition of methanol has a strong effect on the HF-LPME extraction efficiency. Other significant parameters affecting the extraction efficiency of HF-LPME were also studied. HF-LPME was effective to isolate the analytes from the complex matrix. Under the optimized conditions, the detection limits of the proposed method varied from 15.2 to 40.5 ng/L. In general, the relative standard deviations (RSDs) were less than 10%. Good linearity was obtained with the correlation coefficients all better than 0.999. The proposed method is simple, quick, few microliters of organic solvent required, and is especially suitable for the analysis of the real sample with small amount available. The overall process of HF-LPME with GC-ICP-MS was applied successfully for the determination of polybrominated diphenyl ethers (PBDEs) in environmental and spiked human serum samples, and the results were satisfactory.

Optimization and application of ICPMS with dynamic reaction cell for precise determination of 44Ca/40Ca isotope ratios.

PubMed

Boulyga, Sergei F; Klötzli, Urs; Stingeder, Gerhard; Prohaska, Thomas

2007-10-15

An inductively coupled plasma mass spectrometer with dynamic reaction cell (ICP-DRC-MS) was optimized for determining (44)Ca/(40)Ca isotope ratios in aqueous solutions with respect to (i) repeatability, (ii) robustness, and (iii) stability. Ammonia as reaction gas allowed both the removal of (40)Ar+ interference on (40)Ca+ and collisional damping of ion density fluctuations of an ion beam extracted from an ICP. The effect of laboratory conditions as well as ICP-DRC-MS parameters such a nebulizer gas flow rate, rf power, lens potential, dwell time, or DRC parameters on precision and mass bias was studied. Precision (calculated using the "unbiased" or "n - 1" method) of a single isotope ratio measurement of a 60 ng g(-1) calcium solution (analysis time of 6 min) is routinely achievable in the range of 0.03-0.05%, which corresponded to the standard error of the mean value (n = 6) of 0.012-0.020%. These experimentally observed RSDs were close to theoretical precision values given by counting statistics. Accuracy of measured isotope ratios was assessed by comparative measurements of the same samples by ICP-DRC-MS and thermal ionization mass spectrometry (TIMS) by using isotope dilution with a (43)Ca-(48)Ca double spike. The analysis time in both cases was 1 h per analysis (10 blocks, each 6 min). The delta(44)Ca values measured by TIMS and ICP-DRC-MS with double-spike calibration in two samples (Ca ICP standard solution and digested NIST 1486 bone meal) coincided within the obtained precision. Although the applied isotope dilution with (43)Ca-(48)Ca double-spike compensates for time-dependent deviations of mass bias and allows achieving accurate results, this approach makes it necessary to measure an additional isotope pair, reducing the overall analysis time per isotope or increasing the total analysis time. Further development of external calibration by using a bracketing method would allow a wider use of ICP-DRC-MS for routine calcium isotopic measurements, but it still requires particular software or hardware improvements aimed at reliable control of environmental effects, which might influence signal stability in ICP-DRC-MS and serve as potential uncertainty sources in isotope ratio measurements.

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.

Specific pathways for the incorporation of dissolved barium and molybdenum into the bivalve shell: an isotopic tracer approach in the juvenile Great Scallop (Pecten maximus).

PubMed

Tabouret, Hélène; Pomerleau, Sébastien; Jolivet, Aurélie; Pécheyran, Christophe; Riso, Ricardo; Thébault, Julien; Chauvaud, Laurent; Amouroux, David

2012-07-01

Dissolved barium and molybdenum incorporation in the calcite shell was investigated in the Great Scallop Pecten maximus. Sixty six individuals were exposed for 16 days to two successive dissolved Ba and Mo concentrations accurately differentiated by two different isotopic enrichments (⁹⁷Mo, ⁹⁵Mo; ¹³⁵Ba, ¹³⁷Ba). Soft tissue and shell isotopic composition were determined respectively by quantitative ICP-MS (Inductively Coupled Plasma Mass Spectrometer) and laser ablation--ICP-MS. Results from Ba enrichment indicate the direct incorporation of dissolved Ba into the shell in proportion to the levels in the water in which they grew with a 6-8 day delay. The low spike contributions and the low partition coefficient (D(Mo) = 0.0049 ± 0.0013), show that neither the soft tissue nor the shell were significantly sensitive to Mo enrichment. These results eliminate direct Mo shell enrichment by the dissolved phase, and favour a trophic uptake that will be investigated using the successive isotopic enrichment approach developed in this study. Copyright © 2012 Elsevier Ltd. All rights reserved.

Development of a remote laser-induced breakdown spectroscopy system for investigation of calcified tissue samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hrdlicka, Ales; Prokes, Lubomir; Stankova, Alice

2010-05-01

The development of a remote laser-induced breakdown spectroscopy (LIBS) setup with an off-axis Newtonian collection optics, Galilean-based focusing telescope, and a 532 nm flattop laser beam source is presented. The device was tested at a 6 m distance on a slice of bone to simulate its possible use in the field, e.g., during archaeological excavations. It is shown that this setup is sufficiently sensitive to both major (P, Mg) and minor elements (Na, Zn, Sr). The measured quantities of Mg, Zn, and Sr correspond to the values obtained by reference laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) measurements within an approximatelymore » 20% range of uncertainty. A single point calibration was performed by use of a bone meal standard . The radial element distribution is almost invariable by use of LA-ICP-MS, whereas the LIBS measurement showed a strong dependence on the sample porosity. Based on these results, this remote LIBS setup with a relatively large (350 mm) collecting mirror is capable of semiquantitative analysis at the level of units of mg kg{sup -1}.« less

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 rice wine samples ranged between 95.5 and 102.8%. Furthermore, the determined contents of Cd and Pb in a certified reference material of red wine (GBW 10031) and a quality control test material of wine (FAPAS T07163QC) by the proposed method were in fairly good accordance with the certified/assigned values. All results verified the accuracy of our method.

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

PubMed

Odegård, M; Mansfeld, J; Dundas, S H

2001-08-01

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

Variation in elemental intensities among teeth and between pre- and postnatal regions of enamel.

PubMed

Dolphin, Alexis E; Goodman, Alan H; Amarasiriwardena, Dulasiri D

2005-12-01

Microspatial analyses of the trace element composition of dental enamel are made possible using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Fine spatial resolution, multielement capabilities, and minimal sample destruction make this technique particularly well-suited for documenting the distribution of elements in sequentially calcifying layers of enamel. Because deciduous enamel forms from week 13 in utero up to 9 months postnatally (thereafter essentially becoming inert), the application of LA-ICP-MS allows for the retrospective measurement of prenatal and early postnatal trace-element uptake during a critical period of child development. In this study, we compared intra- and intertooth intensities of 25Mg, 57Fe, 66Zn, 68Zn, 88Sr, 138Ba, and 208Pb via LA-ICP-MS of 38 exfoliated deciduous incisors and canines donated by 36 participants in the Solís Valley Mexico Nutrition Collaborative Research Support Program (NCRSP). Pre- and postnatal comparisons within teeth showed significant increases (P < 0.001) and greater variation in the abundance of all isotopes in postnatal enamel, with the exception of a decrease in 25Mg (P < 0.001) and constant values for 88Sr (P = 0.681). Conversely, comparisons by tooth type and mouth quadrant revealed few significant differences between teeth of the same individual. We argue that more variation in the trace element composition of teeth occurs across developmental areas within a tooth than among different teeth of the same person. This study further demonstrates that sequentially calcifying areas of enamel have different chemical concentrations. The results support the use of microspatial analyses of enamel for understanding changes in nutrition, pollution, and residence. 2005 Wiley-Liss, Inc.

Isotope-ratio measurements of lead in NIST standard reference materials by multiple-collector inductively coupled plasma mass spectrometry.

PubMed

Platzner, I; Ehrlich, S; Halicz, L

2001-07-01

The capability of a second-generation Nu Instruments multiple collector inductively coupled plasma mass spectrometer (MC-ICP-MS) has been evaluated for precise and accurate isotope-ratio determinations of lead. Essentially the mass spectrometer is a double-focusing instrument of Nier-Johnson analyzer geometry equipped with a newly designed variable-dispersion ion optical device, enabling the measured ion beams to be focused into a fixed array of Faraday collectors and an ion-counting assembly. NIST SRM Pb 981, 982, and 983 isotopic standards were used. Addition of thallium to the lead standards and subsequent simultaneous measurement of the thallium and lead isotopes enabled correction for mass discrimination, by use of the exponential correction law and 205Tl/203Tl = 2.3875. Six measurements of SRM Pb-982 furnished the results 206Pb/204Pb = 36.7326(68), 207Pb/204Pb = 17.1543(30), 208Pb/204Pb = 36.7249(69), 207Pb/206Pb = 0.46700(1), and 208Pb/206Pb = 0.99979(2); the NIST-certified values were 36.738(37), 17.159(25), 36.744(50), 0.46707(20), and 1.00016(36), respectively. Direct isotope lead analysis in silicates can be performed without any chemical separation. NIST SRM 610 glass was dissolved and introduced into the MC-ICP-MS by means of a micro concentric nebulizer. The ratios observed were in excellent agreement with previously reported data obtained by TIMS and laser ablation MC-ICP-MS, despite the high Ca/Pb concentration ratio (200/1) and the presence of many other elements at levels comparable with that of lead. Approximately 0.2 microg lead are sufficient for isotope analysis with ratio uncertainties between 240 and 530 ppm.

Trace element-protein interactions in endolymph from the inner ear of fish: implications for environmental reconstructions using fish otolith chemistry.

PubMed

Thomas, Oliver R B; Ganio, Katherine; Roberts, Blaine R; Swearer, Stephen E

2017-03-22

Otoliths, the biomineralised hearing "ear stones" from the inner ear of fish, grow throughout the lifespan of an individual, with deposition of alternating calciferous and proteinaceous bands occurring daily. Trace element : calcium ratios within daily increments measured by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) are often used in fisheries science to reconstruct environmental histories. There is, however, considerable uncertainty as to which elements are interacting with either the proteinaceous or calciferous zones of the otolith, and thus their utility as indicators of environmental change. To answer this, we used size exclusion chromatography-inductively coupled plasma-mass spectrometry (SEC-ICP-MS) of endolymph, the otolith growth medium, to determine the binding interactions for a range of elements. In addition, we used solution ICP-MS to quantify element concentrations in paired otolith and endolymph samples and determined relative enrichment factors for each. We found 12 elements that are present only in the proteinaceous fraction, 6 that are present only in the salt fraction, and 4 that are present in both. These findings have important implications for the reconstruction of environmental histories based on changes in otolith elemental composition: (1) elements occurring only in the salt fraction are most likely to reflect changes in the physico-chemical environment experienced during life; (2) elements occurring only in the proteinaceous fraction are more likely to reflect physiological rather than environmental events; and (3) elements occurring in both the salt and proteinaceous fractions are likely to be informative about both endogenous and exogenous processes, potentially reducing their utility in environmental reconstructions.

Investigation of mass dependence effects for the accurate determination of molybdenum isotope amount ratios by MC-ICP-MS using synthetic isotope mixtures.

PubMed

Malinovsky, Dmitry; Dunn, Philip J H; Petrov, Panayot; Goenaga-Infante, Heidi

2015-01-01

Methodology for absolute Mo isotope amount ratio measurements by multicollector inductively coupled plasma-mass spectrometry (MC-ICP-MS) using calibration with synthetic isotope mixtures (SIMs) is presented. For the first time, synthetic isotope mixtures prepared from seven commercially available isotopically enriched molybdenum metal powders ((92)Mo, (94)Mo, (95)Mo, (96)Mo, (97)Mo, (98)Mo, and (100)Mo) are used to investigate whether instrumental mass discrimination of Mo isotopes in MC-ICP-MS is consistent with mass-dependent isotope distribution. The parent materials were dissolved and mixed as solutions to obtain mixtures with accurately known isotope amount ratios. The level of elemental impurities in the isotopically enriched molybdenum metal powders was quantified by ICP-MS by using both high-resolution and reaction cell instruments to completely resolve spectral interferences. The Mo isotope amount ratio values with expanded uncertainty (k = 2), determined by MC-ICP-MS for a high-purity Mo rod from Johnson Matthey, were as follows: (92)Mo/(95)Mo = 0.9235(9), (94)Mo/(95)Mo = 0.5785(8), (96)Mo/(95)Mo = 1.0503(9), (97)Mo/(95)Mo = 0.6033(6), (98)Mo/(95)Mo = 1.5291(20), and (100)Mo/(95)Mo = 0.6130(7). A full uncertainty budget for the measurements is presented which shows that the largest contribution to the uncertainty budget comes from correction for elemental impurities (∼51%), followed by the contribution from weighing operations (∼26 %). The atomic weight of molybdenum was calculated to be 95.947(2); the uncertainty in parentheses is expanded uncertainty with the coverage factor of 2. A particular advantage of the developed method is that calibration factors for all six Mo isotope amount ratios, involving the (95)Mo isotope, were experimentally determined. This allows avoiding any assumption on mass-dependent isotope fractions in MC-ICP-MS, inherent to the method of double spike previously used for Mo isotope amount ratio measurements. However, data obtained in this study show that instrumental mass discrimination in MC-ICP-MS is consistent with mass-dependent Mo isotope fractionation. This was demonstrated by a good agreement between experimentally obtained and theoretically expected values of the exponent of isotope fractionation, β, for each triad of Mo isotopes.

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.

Ir and Rare Earth's Elements determination by Neutron Activation Analysis and ICP - MS in soil samples

NASA Astrophysics Data System (ADS)

Salvini, A.; Cattadori, C.; Broggini, C.; Cagnazzo, M.; Ori, Gian Gabriele; Nisi, S.; Borio, A.; Manera, S.

2006-05-01

The platinum metals depleted in the earth's crust are relative to their cosmic abundance; concentration of these elements in sediments may thus indicate influxes of extraterrestrial material. Analysis of these parameters are done easily by Neutron Activation Analysis (NAA) and comparative results with ICP-MS technique show a good match. Results, adjust parameters and limits of this method will be displayed in tables.

Determination of Silicon in Hydrazine

NASA Technical Reports Server (NTRS)

McClure, Mark B.; Mast, Dion; Greene, Ben; Maes, Miguel J.

2006-01-01

Inductively coupled plasma-mass spectrometry (ICP-MS) is a highly sensitive technique sometimes used for the trace determination of silicon at a mass-to-charge (m/z) ratio of 28, the most abundant natural isotope of silicon. Unfortunately, ICP-MS is unable to differentiate between other sources of m/z 28 and false positive results for silicon will result when other sources of m/z 28 are present. Nitrogen was a major source of m/z 28 and contributes to the m/z 28 signal when hydrazine sample or nitric acid preservative is introduced into the plasma. Accordingly, this work was performed to develop a sample preparation step coupled with an ICP-MS analysis that minimized non-silicon sources of m/z 28. In the preparatory step of this method, the hydrazine sample was first decomposed predominately to nitrogen gas and water with copper-catalyzed hydrogen peroxide. In the analysis step, ICP-MS was used without nitric acid preservative in samples or standards. Glass, a potential source of silicon contamination, was also avoided where possible. The method was sensitive, accurate, and reliable for the determination of silicon in monopropellant grade hydrazine (MPH) in AF-E-332 elastomer leaching tests. Results for silicon in MPH were comparable to those reported in the literature for other studies.

Comparison of Dilution, Filtration, and Microwave Digestion Sample Pretreatments in Elemental Profiling of Wine by ICP-MS.

PubMed

Godshaw, Joshua; Hopfer, Helene; Nelson, Jenny; Ebeler, Susan E

2017-09-25

Wine elemental composition varies by cultivar, geographic origin, viticultural and enological practices, and is often used for authenticity validation. Elemental analysis of wine by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is challenging due to the potential for non-spectral interferences and plasma instability arising from organic matrix components. Sample preparation mitigates these interferences, however, conflicting recommendations of best practices in ICP-MS analysis of wine have been reported. This study compared direct dilution, microwave-assisted acid digestion, and two filtration sample pretreatments, acidification prior to filtration and filtration followed by acidification, in elemental profiling of one white and three red table wines by ICP-MS. Of 43 monitored isotopes, 37 varied by sample preparation method, with significantly higher results of 17 isotopes in the microwave-digested samples. Both filtration treatments resulted in lower results for 11 isotopes compared to the other methods. Finally, isotope dilution determination of copper based on natural abundances and the 63 Cu: 65 Cu instrument response ratio agreed with external calibration and confirmed a significant sample preparation effect. Overall, microwave digestion did not compare favorably, and direct dilution was found to provide the best compromise between ease of use and result accuracy and precision, although all preparation strategies were able to differentiate the wines.

Elemental analysis of forensic glasses by inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Almirall, Jose R.; Duckworth, Douglas C.; Bayne, Charles K.; Morton, Sherman A.; Smith, David H.; Koons, Robert D.; Furton, Kenneth G.

1999-02-01

Flat glass is a common type of evidence collected from the scenes of crimes such as burglaries, vandalism, and hit-and- run accidents. The usefulness of such evidence lies in the ability to associate the glass from the scene (or a suspect) to the original source. Physical and chemical analysis of the glass can be used for discrimination between the possible sources of glass. If the sample is large enough, physical attributes such as fracture matches, density, color, and thickness can be employed for comparison between a recovered fragment(s) to the suspect source. More commonly, refractive index (RI) comparisons are employed. Due to the improved control over glass manufacturing processes, RI values often cannot differentiate glasses where approximately 6 - 9% of casework samples are not expected to be distinguished by RI alone even if they originated from different sources. Employing methods such as NAA, XRF, ICP-AES, and ICP-MS for the comparison of trace elemental compositions has been shown to be more discriminating than RI comparisons. The multielement capability and the sensitivity of ICP-AES and ICP-MS provide for excellent discrimination power. In this work, the sources of variability in ICP-MS of glass analysis are investigated to determine possible sources of variation. The sources of variation examined include errors due to sample preparation, instrument accuracy and precision, and interlaboratory reproducibility. Other sources of variation include inhomogeneity across a sheet of glass from the same source. Analysis of variance has been applied to our ICP-MS analysis of NIST standards and to the interlaboratory comparisons of float glass samples collected across a sheet in a production facility. The results of these experiments allows for a more accurate interpretation of forensic glass data and a better understanding of the discriminating power (absolute and practical) of ICP-MS.

Rapid screening of heavy metals and trace elements in environmental samples using portable X-ray fluorescence spectrometer, A comparative study

PubMed Central

McComb, Jacqueline Q.; Rogers, Christian; Han, Fengxiang X.; Tchounwou, Paul B.

2014-01-01

With industrialization, great amounts of trace elements and heavy metals have been excavated and released on the surface of the earth and dissipated into the environments. Rapid screening technology for detecting major and trace elements as well as heavy metals in variety of environmental samples is most desired. The objectives of this study were to determine the detection limits, accuracy, repeatability and efficiency of a X-ray fluorescence spectrometer (Niton XRF analyzer) in comparison with the traditional analytical methods, inductively coupled plasma optical emission spectrometer (ICP-OES) and inductively coupled plasma optical emission spectrometer (ICP-MS) in screening of major and trace elements of environmental samples including estuary soils and sediments, contaminated soils, and biological samples. XRF is a fast and non-destructive method in measuring the total concentration of multi--elements simultaneously. Contrary to ICP-OES and ICP-MS, XRF analyzer is characterized by the limited preparation required for solid samples, non-destructive analysis, increased total speed and high throughout, the decreased production of hazardous waste and the low running costs as well as multi-elemental determination and portability in the fields. The current comparative study demonstrates that XRF is a good rapid non-destructive method for contaminated soils, sediments and biological samples containing higher concentrations of major and trace elements. Unfortunately, XRF does not have sensitive detection limits of most major and trace elements as ICP-OES or ICP-MS but it may serve as a rapid screening tool for locating hot spots of uncontaminated field soils and sediments. PMID:25861136

Evaluation of the accuracy of the determination of lead isotope ratios in wine by ICP MS using quadrupole, multicollector magnetic sector and time-of-flight analyzers.

PubMed

Barbaste, M; Halicz, L; Galy, A; Medina, B; Emteborg, H; C Adams, F; Lobinski, R

2001-04-12

Different mass analysers [(quadrupole (Q), time-of-flight (TOF) and multicollector (MC) sector-field (SF)] of ions produced in an inductively coupled plasma were evaluated for the determination of lead isotope ratios in wine samples. A population of 20 wines of different origin including two reference wines from the EC Standards, Measurement and Testing Programme with concentrations varying between 7-140 mug Pb l(-1) was investigated. Wines were analyzed directly by Q ICP MS and MC ICP MS. The poor sensitivity of the TOF instrument, further aggravated by matrix signal suppression, did not allow the acquisition of data for wine samples that contained less than 50 mug l(-1) in the direct sample introduction mode. The separation and preconcentration of lead were therefore required. The precision obtained for the (206)Pb/(207)Pb and (208)Pb/(206)Pb were similar and equal to 0.14-2.7% for Q ICP MS, 0.04-0.17% for TOF ICP MS and 0.01-0.12% for MC ICP MS. The precision for (206)Pb/(204)Pb was 0.44-5.29, 0.15-1.7, 0.08-1.6%, respectively. On the level of accuracy, the data from TOF ICP MS and MC ICP MS were in good agreement. The accuracy of Q ICP MS data was judged satisfactory in comparison with the other techniques but their poor precision was a significant obstacle on the way of using these data for the determination of the geographic origin of wine.

In-situ Sr isotopic measurement of scheelite using fs-LA-MC-ICPMS

NASA Astrophysics Data System (ADS)

Li, Chao; Zhou, Limin; Zhao, Zheng; Zhang, Zhiyuan; Zhao, Hong; Li, Xinwei; Qu, Wenjun

2018-07-01

Scheelite is one of the main ore minerals in tungsten deposits, and Sr isotopic compositions of scheelite can be used to examine the petrogenesis of igneous rocks and fluid metasomatism in mineralization processes. Both thermal ionization mass spectrometer (TIMS) and femsecond laser ablation multi-collector inductively coupled plasma mass spectrometer (fs-LA-MC-ICP-MS) have been applied to analyze Sr isotopic compositions in scheelite. Here we describe a LA-MC-ICP-MS technique which can obtain in-situ, accurate, high precision 87Sr/86Sr ratios from 20 to 50 μm scheelite in line mode without requiring time-consuming mineral separation and pre-chemical procedures. We found that Ca dimers and Ca argides do not detectably affect the obtained 87Sr/86Sr ratios, and the adopted protocol overcomes interferences from Kr+, Rb+, Er2+ and Yb2+. The results of three MPI-DING reference glasses (KL2-G, ML3B-G and StHs6/80-G) are consistent with the recommended values. Here we show that the values of 87Sr/86Sr are relatively homogeneous for two scheelites from quartz veins, and are comparable to the values determined by a traditional solution method. Hence, these two scheelite samples have the potential to be reference materials for Sr isotopic determination by LA-MC-ICP-MS. To illustrate the utility of the technique, Sr isotopes of scheelites from three different types of tungsten deposits of South China are documented. The 87Sr/86Sr of scheelite from granite-related veinlet-disseminated and porphyry tungsten deposits varies systematically, showing a positive correlation between Sr content and 87Sr/86Sr ratios. These micrometer scale inhomogeneities could be explained by mixing of two components, reflecting intense fluid metasomatism during mineralization processes. High 87Sr/86Sr ratios were obtained for the scheelite samples from a quartz vein type tungsten deposit, indicating that the late stage ore-forming fluid was mainly derived from the surrounding strata. These examples show that in-situ Sr isotopic measurement of scheelite is a powerful tool to decipher the degree of fluid-rock interaction in ore-forming processes.

Detection of beryllium treatment of natural sapphires by NRA

NASA Astrophysics Data System (ADS)

Gutiérrez, P. C.; Ynsa, M.-D.; Climent-Font, A.; Calligaro, T.

2010-06-01

Since the 1990's, artificial treatment of natural sapphires (Al 2O 3 crystals coloured by impurities) by diffusion of beryllium at high temperature has become a growing practice. This process permits to enhance the colour of these gemstones, and thus to increase their value. Detection of such a treatment - diffusion of tens of μg/g of beryllium in Al 2O 3 crystals - is usually achieved using high sensitivity techniques like laser-ablation inductively coupled plasma mass spectrometry (LA-ICP/MS) or laser-induced breakdown spectrometry (LIBS) which are unfortunately micro-destructive (leaving 50-100-μm diameter craters on the gems). The simple and non-destructive alternative method proposed in this work is based on the nuclear reaction 9Be(α, nγ) 12C with an external helium ion beam impinging on the gem directly placed in air. The 4439 keV prompt γ-ray tagging Be atoms are detected with a high efficiency bismuth germanate scintillator. Beam dose is monitored using the 2235 keV prompt γ-ray produced during irradiation by the aluminium of the sapphire matrix through the 27Al(α, pγ) 30Si nuclear reaction. The method is tested on a series of Be-treated sapphires previously analyzed by LA-ICP/MS to determine the optimal conditions to obtain a peak to background appropriate to reach the required μg/g sensitivity. Using a 2.8-MeV external He beam and a beam dose of 200 μC, beryllium concentrations from 5 to 16 μg/g have been measured in the samples, with a detection limit of 1 μg/g.

Measurement of technetium-99 in Marshall Islands soil samples by ICP-MS

PubMed

Tagami; Uchida; Hamilton; Robison

2000-07-01

Extraction techniques for recovery of technetium-99 (99Tc) for Inductively Coupled Plasma Mass Spectrometry (ICP-MS) measurements were evaluated using soil samples collected from the Marshall Islands. The results of three different extraction techniques were compared: (MI) acid leaching of Tc from ashed soil; (M2) acid leaching of Tc from raw dry soil; and (M3) Tc volatilization from ashed soil using a combustion apparatus. Total Tc recoveries varied considerably between the extraction techniques but each method yielded similar analytical results for 99Tc. Applications of these extraction techniques to a series of environmental samples and ICP-MS measurements have yielded first data on the 99Tc content of Marshall Islands soil samples contaminated with close-in radioactive fallout from nuclear weapons testing. The 99Tc activity concentration in the soil samples ranged between 0.1 and 1.1 mBq g(-1) dry weight (dw). The limit of detection for 99Tc by ICP-MS was 0.17 mBq per sample or 0.014 mBq g(-1) dw under standard operating conditions.

Feasibility of Rare Earth Element Determination in Low Concentration in Crude Oil: Direct Sampling Electrothermal Vaporization-Inductively Coupled Plasma Mass Spectrometry.

PubMed

Silva, Jussiane Souza; Schneider Henn, Alessandra; Dressler, Valderi Luiz; Mello, Paola Azevedo; Flores, Erico Marlon Moraes

2018-06-05

A comprehensive study was developed showing the feasibility of determination of rare earth elements (REE) in low concentration in crude oil by using direct sampling electrothermal vaporization system coupled to inductively coupled plasma mass spectrometry (ETV-ICP-MS). The effect of organic modifier on the REE signal was evaluated and the use of 6 mg of citric acid allowed calibration using aqueous reference solutions (selected pyrolysis and vaporization temperatures were 700 and 2200 °C, respectively). Because of the facility of REE in forming refractory compounds inside the graphite furnace during the heating step, the use of a modifier gas (Freon R-12, 3.0 mL min -1 ) was necessary to allow quantitative vaporization of these elements. A flow rate of 0.40 L min -1 was selected for both bypass and carrier gases. Under optimized conditions, the influence of sample mass was evaluated, and even using a relatively high mass of crude oil (up to 18 mg), accurate results were obtained. The accuracy was evaluated by the comparison of results by ETV-ICP-MS with those obtained by ICP-MS with ultrasonic nebulizer (USN) after high-pressure microwave-assisted wet digestion (MAWD) and microwave-induced combustion (MIC) and no statistical difference was observed between the results. The limits of quantification for REE by ETV-ICP-MS were lower (0.02-0.8 ng g -1 ) than those obtained by USN-ICP-MS after MAWD and MIC (0.6-5.1 ng g -1 ). Negligible blank values and relative standard deviations lower than 12% show the feasibility of the proposed ETV-ICP-MS method for routine analysis of crude oil.

Molecular speciation and tissue compartmentation of zinc in durum wheat grains with contrasting nutritional status.

PubMed

Persson, Daniel Pergament; de Bang, Thomas C; Pedas, Pai R; Kutman, Umit Baris; Cakmak, Ismail; Andersen, Birgit; Finnie, Christine; Schjoerring, Jan K; Husted, Søren

2016-09-01

Low concentration of zinc (Zn) in the endosperm of cereals is a major factor contributing to Zn deficiency in human populations. We have investigated how combined Zn and nitrogen (N) fertilization affects the speciation and localization of Zn in durum wheat (Triticum durum). Zn-binding proteins were analysed with liquid chromatography ICP-MS and Orbitrap MS(2) , respectively. Laser ablation ICP-MS with simultaneous Zn, sulphur (S) and phosphorus (P) detection was used for bioimaging of Zn and its potential ligands. Increasing the Zn and N supply had a major impact on the Zn concentration in the endosperm, reaching concentrations higher than current breeding targets. The S concentration also increased, but S was only partly co-localized with Zn. The mutual Zn and S enrichment was reflected in substantially more Zn bound to small cysteine-rich proteins (apparent size 10-30 kDa), whereas the response of larger proteins (apparent size > 50 kDa) was only modest. Most of the Zn-responsive proteins were associated with redox- and stress-related processes. This study offers a methodological platform to deepen the understanding of processes behind endosperm Zn enrichment. Novel information is provided on how the localization and speciation of Zn is modified during Zn biofortification of grains. © 2016 The Authors. New Phytologist © 2016 New Phytologist Trust.

Direct uranium isotope ratio analysis of single micrometer-sized glass particles

PubMed Central

Kappel, Stefanie; Boulyga, Sergei F.; Prohaska, Thomas

2012-01-01

We present the application of nanosecond laser ablation (LA) coupled to a ‘Nu Plasma HR’ multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) for the direct analysis of U isotope ratios in single, 10–20 μm-sized, U-doped glass particles. Method development included studies with respect to (1) external correction of the measured U isotope ratios in glass particles, (2) the applied laser ablation carrier gas (i.e. Ar versus He) and (3) the accurate determination of lower abundant 236U/238U isotope ratios (i.e. 10−5). In addition, a data processing procedure was developed for evaluation of transient signals, which is of potential use for routine application of the developed method. We demonstrate that the developed method is reliable and well suited for determining U isotope ratios of individual particles. Analyses of twenty-eight S1 glass particles, measured under optimized conditions, yielded average biases of less than 0.6% from the certified values for 234U/238U and 235U/238U ratios. Experimental results obtained for 236U/238U isotope ratios deviated by less than −2.5% from the certified values. Expanded relative total combined standard uncertainties Uc (k = 2) of 2.6%, 1.4% and 5.8% were calculated for 234U/238U, 235U/238U and 236U/238U, respectively. PMID:22595724

Direct uranium isotope ratio analysis of single micrometer-sized glass particles.

PubMed

Kappel, Stefanie; Boulyga, Sergei F; Prohaska, Thomas

2012-11-01

We present the application of nanosecond laser ablation (LA) coupled to a 'Nu Plasma HR' multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) for the direct analysis of U isotope ratios in single, 10-20 μm-sized, U-doped glass particles. Method development included studies with respect to (1) external correction of the measured U isotope ratios in glass particles, (2) the applied laser ablation carrier gas (i.e. Ar versus He) and (3) the accurate determination of lower abundant (236)U/(238)U isotope ratios (i.e. 10(-5)). In addition, a data processing procedure was developed for evaluation of transient signals, which is of potential use for routine application of the developed method. We demonstrate that the developed method is reliable and well suited for determining U isotope ratios of individual particles. Analyses of twenty-eight S1 glass particles, measured under optimized conditions, yielded average biases of less than 0.6% from the certified values for (234)U/(238)U and (235)U/(238)U ratios. Experimental results obtained for (236)U/(238)U isotope ratios deviated by less than -2.5% from the certified values. Expanded relative total combined standard uncertainties U(c) (k = 2) of 2.6%, 1.4% and 5.8% were calculated for (234)U/(238)U, (235)U/(238)U and (236)U/(238)U, respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

Preparation of hair for measurement of elements by inductively coupled plasma-mass spectrometry (ICP-MS).

PubMed

Puchyr, R F; Bass, D A; Gajewski, R; Calvin, M; Marquardt, W; Urek, K; Druyan, M E; Quig, D

1998-06-01

The preparation of hair for the determination of elements is a critical component of the analysis procedure. Open-beaker, closed-vessel microwave, and flowthrough microwave digestion are methods that have been used for sample preparation and are discussed. A new digestion method for use with inductively coupled plasma-mass spectrometry (ICP-MS) has been developed. The method uses 0.2 g of hair and 3 mL of concentrated nitric acid in an atmospheric pressure-low-temperature microwave digestion (APLTMD) system. This preparation method is useful in handling a large numbers of samples per day and may be adapted to hair sample weights ranging from 0.08 to 0.3 g. After digestion, samples are analyzed by ICP-MS to determine the concentration of Li, Be, B, Na, Mg, Al, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ge, As, Se, Rb, Sr, Zr, Mo, Pd, Ag, Cd, Sn, Sb, I, Cs, Ba, Pt, Au, Hg, Tl, Pb, Bi, Th, and U. Benefits of the APLTMD include reduced contamination and sample handling, and increased precision, reliability, and sample throughput.

Elemental Analysis in Biological Matrices Using ICP-MS.

PubMed

Hansen, Matthew N; Clogston, Jeffrey D

2018-01-01

The increasing exploration of metallic nanoparticles for use as cancer therapeutic agents necessitates a sensitive technique to track the clearance and distribution of the material once introduced into a living system. Inductively coupled plasma mass spectrometry (ICP-MS) provides a sensitive and selective tool for tracking the distribution of metal components from these nanotherapeutics. This chapter presents a standardized method for processing biological matrices, ensuring complete homogenization of tissues, and outlines the preparation of appropriate standards and controls. The method described herein utilized gold nanoparticle-treated samples; however, the method can easily be applied to the analysis of other metals.

Novel method for metalloproteins determination in human breast milk by size exclusion chromatography coupled to inductively coupled plasma mass spectrometry.

PubMed

Acosta, Mariano; Torres, Sabier; Mariño-Repizo, Leonardo; Martinez, Luis D; Gil, Raúl A

2018-06-02

Levels of essential metals in human breast milk (HBM) have been determined by different analytical techniques, but there is few woks about human whey milk fractions. However, the current trend lies in metalloproteomic and identification of different metalloproteins. In this sense, native separative techniques (N-PAGE and SEC) coupled to ICP-MS provide us with valuable information. Besides it is necessary the development of new methodologies in order to determine with accuracy and precision the profile of such metals and metalloproteins in the different whey protein fractions of HBM. Thus, the aim of this work was to develop a new method for metals and metalloproteins determination by SEC-ICP-MS in whey protein fractions of HBM. Human whey fractions were obtained of HBM samples by ultracentrifugation. Then, protein fractions of whey milk were separated by SEC coupled to ICP-MS for metalloproteins and Mn, Co, Cu and Se quantification. Besides, protein profile of whey milk was determined by N-PAGE and computer assisted image analysis. SEC-ICP-MS results indicated that first and second protein fractions showed detectable levels of the Mn, Co, Cu, and Se. Protein profile determined by N-PAGE and image analysis showed that molecular weight of protein fractions ranged between 68,878-1,228.277 Da. In this work, metalloproteins were analyzed by SEC coupled to ICP-MS, with adequate sensitivity and accuracy. Our study has shown the presence of Mn, Co, Cu and Se bound to two protein fractions in whey milk of HBM. Metals levels analyzed were within the ranges reported in the literature. Copyright © 2018 Elsevier B.V. All rights reserved.

An Evaluation of Unit and ½ Mass Correction Approaches as a Means of Minimizing the False Positives Produced by M+2 species in US EPA Method 200.8 using ICP-MS

EPA Science Inventory

Rare earth elements (REE) and certain alkaline earths can produce M+2 interferences in ICP-MS because they have sufficiently low second ionization energies. Four REEs (150Sm, 150Nd, 156Gd and 156Dy) produce false positives on 75As and 78Se and 132Ba can produce a false positive ...

Current role of ICP-MS in clinical toxicology and forensic toxicology: a metallic profile.

PubMed

Goullé, Jean-Pierre; Saussereau, Elodie; Mahieu, Loïc; Guerbet, Michel

2014-08-01

As metal/metalloid exposure is inevitable owing to its omnipresence, it may exert toxicity in humans. Recent advances in metal/metalloid analysis have been made moving from flame atomic absorption spectrometry and electrothermal atomic absorption spectrometry to the multi-elemental inductively coupled plasma (ICP) techniques as ICP atomic emission spectrometry and ICP-MS. ICP-MS has now emerged as a major technique in inorganic analytical chemistry owing to its flexibility, high sensitivity and good reproducibility. This in depth review explores the ICP-MS metallic profile in human toxicology. It is now routinely used and of great importance, in clinical toxicology and forensic toxicology to explore biological matrices, specifically whole blood, plasma, urine, hair, nail, biopsy samples and tissues.

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

PubMed

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

2015-09-01

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

Lithium loss in the solid electrolyte interphase: Lithium quantification of aged lithium ion battery graphite electrodes by means of laser ablation inductively coupled plasma mass spectrometry and inductively coupled plasma optical emission spectroscopy

NASA Astrophysics Data System (ADS)

Schwieters, Timo; Evertz, Marco; Mense, Maximilian; Winter, Martin; Nowak, Sascha

2017-07-01

In this work we present a new method using LA-ICP-MS to quantitatively determine the lithium content in aged graphite electrodes of a lithium ion battery (LIB) by performing total depth profiling. Matrix matched solid external standards are prepared using a solid doping approach to avoid elemental fractionation effects during the measurement. The results are compared and matched to the established ICP-OES technique for bulk quantification after performing a microwave assisted acid digestion. The method is applied to aged graphite electrodes in order to determine the lithium immobilization (= "Li loss") in the solid electrolyte interphase after the first cycle of formation. For this, different samples including a reference sample are created to obtain varying thicknesses of the SEI covering the electrode particles. By applying defined charging voltages, an initial lithiation process is performed to obtain specific graphite intercalation compounds (GICs, with target stoichiometries of LiC30, LiC18, LiC12 and LiC6). Afterwards, the graphite electrode is completely discharged to obtain samples without mobile, thus active lithium in its lattice. Taking the amount of lithium into account which originates from the residues of the LiPF6 (dissolved in the carbon components containing electrolyte), it is possible to subtract the amount of lithium in the SEI.

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

PubMed

Konegger-Kappel, Stefanie; Prohaska, Thomas

2016-01-01

Laser ablation-multi-collector-inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) was optimized and investigated with respect to its performance for determining spatially resolved Pu isotopic signatures within radioactive fuel particle clusters. Fuel particles had been emitted from the Chernobyl nuclear power plant (ChNPP) where the 1986 accident occurred and were deposited in the surrounding soil, where weathering processes caused their transformation into radioactive clusters, so-called micro-samples. The size of the investigated micro-samples, which showed surface alpha activities below 40 mBq, ranged from about 200 to 1000 μm. Direct single static point ablations allowed to identify variations of Pu isotopic signatures not only between distinct fuel particle clusters but also within individual clusters. The resolution was limited to 100 to 120 μm as a result of the applied laser ablation spot sizes and the resolving power of the nuclear track radiography methodology that was applied for particle pre-selection. The determined (242)Pu/(239)Pu and (240)Pu/(239)Pu isotope ratios showed a variation from low to high Pu isotope ratios, ranging from 0.007(2) to 0.047(8) for (242)Pu/(239)Pu and from 0.183(13) to 0.577(40) for (240)Pu/(239)Pu. In contrast to other studies, the applied methodology allowed for the first time to display the Pu isotopic distribution in the Chernobyl fallout, which reflects the differences in the spent fuel composition over the reactor core. The measured Pu isotopic signatures are in good agreement with the expected Pu isotopic composition distribution that is typical for a RBMK-1000 reactor, indicating that the analyzed samples are originating from the ill-fated Chernobyl reactor. The average Pu isotope ratios [(240)Pu/(239)Pu = 0.388(86), (242)Pu/(239)Pu = 0.028(11)] that were calculated from all investigated samples (n = 48) correspond well to previously published results of Pu analyses in contaminated samples from the vicinity of the Chernobyl NPP [e.g. (240)Pu/(239)Pu = 0.394(2) and (242)Pu/(239)Pu = 0.027(1); Nunnemann et al. (J Alloys Compd 271-273:45-48, 1998)].

Development of candidate reference materials for the measurement of lead in bone

PubMed Central

Hetter, Katherine M.; Bellis, David J.; Geraghty, Ciaran; Todd, Andrew C.; Parsons, Patrick J.

2010-01-01

The production of modest quantities of candidate bone lead (Pb) reference materials is described, and an optimized production procedure is presented. The reference materials were developed to enable an assessment of the interlaboratory agreement of laboratories measuring Pb in bone; method validation; and for calibration of solid sampling techniques such as laser ablation ICP-MS. Long bones obtained from Pb-dosed and undosed animals were selected to produce four different pools of a candidate powdered bone reference material. The Pb concentrations of these pools reflect both environmental and occupational exposure levels in humans. The animal bones were harvested post mortem, cleaned, defatted, and broken into pieces using the brittle fracture technique at liquid nitrogen temperature. The bone pieces were then ground in a knife mill to produce fragments of 2-mm size. These were further ground in an ultra-centrifugal mill, resulting in finely powdered bone material that was homogenized and then sampled-scooped into vials. Testing for contamination and homogeneity was performed via instrumental methods of analysis. PMID:18421443

Determination of plutonium isotopes (238Pu, 239Pu, 240Pu, 241Pu) in environmental samples using radiochemical separation combined with radiometric and mass spectrometric measurements.

PubMed

Xu, Yihong; Qiao, Jixin; Hou, Xiaolin; Pan, Shaoming; Roos, Per

2014-02-01

This paper reports an analytical method for the determination of plutonium isotopes ((238)Pu, (239)Pu, (240)Pu, (241)Pu) in environmental samples using anion exchange chromatography in combination with extraction chromatography for chemical separation of Pu. Both radiometric methods (liquid scintillation counting and alpha spectrometry) and inductively coupled plasma mass spectrometry (ICP-MS) were applied for the measurement of plutonium isotopes. The decontamination factors for uranium were significantly improved up to 7.5 × 10(5) for 20 g soil compared to the level reported in the literature, this is critical for the measurement of plutonium isotopes using mass spectrometric technique. Although the chemical yield of Pu in the entire procedure is about 55%, the analytical results of IAEA soil 6 and IAEA-367 in this work are in a good agreement with the values reported in the literature or reference values, revealing that the developed method for plutonium determination in environmental samples is reliable. The measurement results of (239+240)Pu by alpha spectrometry agreed very well with the sum of (239)Pu and (240)Pu measured by ICP-MS. ICP-MS can not only measure (239)Pu and (240)Pu separately but also (241)Pu. However, it is impossible to measure (238)Pu using ICP-MS in environmental samples even a decontamination factor as high as 10(6) for uranium was obtained by chemical separation. © 2013 Elsevier B.V. All rights reserved.

Single particle ICP-MS characterization of titanium dioxide, silver, and gold nanoparticles during drinking water treatment.

PubMed

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

2016-02-01

One of the most direct means for human exposure to nanoparticles (NPs) released into the environment is drinking water. Therefore, it is critical to understand the occurrence and fate of NPs in drinking water systems. The objectives of this study were to develop rapid and reliable analytical methods and apply them to investigate the fate and transportation of NPs during drinking water treatments. Rapid single particle ICP-MS (SP-ICP-MS) methods were developed to characterize and quantify titanium-containing, titanium dioxide, silver, and gold NP concentration, size, size distribution, and dissolved metal element concentration in surface water and treated drinking water. The effectiveness of conventional drinking water treatments (including lime softening, alum coagulation, filtration, and disinfection) to remove NPs from surface water was evaluated using six-gang stirrer jar test simulations. The selected NPs were nearly completely (97 ± 3%) removed after lime softening and alum coagulation/activated carbon adsorption treatments. Additionally, source and drinking waters from three large drinking water treatment facilities utilizing similar treatments with the simulation test were collected and analyzed by the SP-ICP-MS methods. Ti-containing particles and dissolved Ti were present in the river water samples, but Ag and Au were not present. Treatments used at each drinking water treatment facility effectively removed over 93% of the Ti-containing particles and dissolved Ti from the source water. Copyright © 2015 Elsevier Ltd. All rights reserved.

Selective hydride generation- cryotrapping- ICP-MS for arsenic speciation analysis at picogram levels: analysis of river and sea water reference materials and human bladder epithelial cells

PubMed Central

Matoušek, Tomáš; Currier, Jenna M.; Trojánková, Nikola; Saunders, R. Jesse; Ishida, María C.; González-Horta, Carmen; Musil, Stanislav; Mester, Zoltán; Stýblo, Miroslav; Dědina, Jiří

2013-01-01

An ultra sensitive method for arsenic (As) speciation analysis based on selective hydride generation (HG) with preconcentration by cryotrapping (CT) and inductively coupled plasma- mass spectrometry (ICP-MS) detection is presented. Determination of valence of the As species is performed by selective HG without prereduction (trivalent species only) or with L-cysteine prereduction (sum of tri- and pentavalent species). Methylated species are resolved on the basis of thermal desorption of formed methyl substituted arsines after collection at −196°C. Limits of detection of 3.4, 0.04, 0.14 and 0.10 pg mL−1 (ppt) were achieved for inorganic As, mono-, di- and trimethylated species, respectively, from a 500 μL sample. Speciation analysis of river water (NRC SLRS-4 and SLRS-5) and sea water (NRC CASS-4, CASS-5 and NASS-5) reference materials certified to contain 0.4 to 1.3 ng mL−1 total As was performed. The concentrations of methylated As species in tens of pg mL−1 range obtained by HG-CT-ICP-MS systems in three laboratories were in excellent agreement and compared well with results of HG-CT-atomic absorption spectrometry and anion exchange liquid chromatography- ICP-MS; sums of detected species agreed well with the certified total As content. HG-CT-ICP-MS method was successfully used for analysis of microsamples of exfoliated bladder epithelial cells isolated from human urine. Here, samples of lysates of 25 to 550 thousand cells contained typically tens pg up to ng of iAs species and from single to hundreds pg of methylated species, well within detection power of the presented method. A significant portion of As in the cells was found in the form of the highly toxic trivalent species. PMID:24014931

Simultaneous quantification of iodine and high valent metals via ICP-MS under acidic conditions in complex matrices.

PubMed

Brix, Kristina; Hein, Christina; Sander, Jonas Michael; Kautenburger, Ralf

2017-05-15

The determination of iodine as a main fission product (especially the isotopes I-129 and I-131) of stored HLW in a disposal beside its distribution as a natural ingredient of many different products like milk, food and seawater is a matter of particular interest. The simultaneous ICP-MS determination of iodine as iodide together with other elements (especially higher valent metal ions) relevant for HLW is analytically very problematic. A reliable ICP-MS quantification of iodide must be performed at neutral or alkaline conditions in contrast to the analysis of metal ions which are determined in acidic pH ranges. Herein, we present a method to solve this problem by changing the iodine speciation resulting in an ICP-MS determination of iodide as iodate. The oxidation from iodide to iodate with sodium hypochlorite at room temperature is a fast and convenient method with flexible reaction time, from one hour up to three days, thus eliminating the disadvantages of quantifying iodine species via ICP-MS. In the analysed concentration range of iodine (0.1-100µgL -1 ) we obtain likely quantitative recovery rates for iodine between 91% and 102% as well as relatively low RSD values (0.3-4.0%). As an additional result, it is possible to measure different other element species in parallel together with the generated iodate, even high valent metals (europium and uranium beside caesium) at recovery rates in the same order of magnitude (93-104%). In addition, the oxidation process operates above pH 7 thus offering a wide pH range for sample preparation. Even analytes in complex matrices, like 5M saline (NaCl) solution or artificial cement pore water (ACW) can be quantified with this robust sample preparation method. Copyright © 2017 Elsevier B.V. All rights reserved.

Prospects and difficulties in TiO₂ nanoparticles analysis in cosmetic and food products using asymmetrical flow field-flow fractionation hyphenated to inductively coupled plasma mass spectrometry.

PubMed

López-Heras, Isabel; Madrid, Yolanda; Cámara, Carmen

2014-06-01

In this work, we proposed an analytical approach based on asymmetrical flow field-flow fractionation combined to an inductively coupled plasma mass spectrometry (AsFlFFF-ICP-MS) for rutile titanium dioxide nanoparticles (TiO2NPs) characterization and quantification in cosmetic and food products. AsFlFFF-ICP-MS separation of TiO2NPs was performed using 0.2% (w/v) SDS, 6% (v/v) methanol at pH 8.7 as the carrier solution. Two problems were addressed during TiO2NPs analysis by AsFlFFF-ICP-MS: size distribution determination and element quantification of the NPs. Two approaches were used for size determination: size calibration using polystyrene latex standards of known sizes and transmission electron microscopy (TEM). A method based on focused sonication for preparing NPs dispersions followed by an on-line external calibration strategy based on AsFlFFF-ICP-MS, using rutile TiO2NPs as standards is presented here for the first time. The developed method suppressed non-specific interactions between NPs and membrane, and overcame possible erroneous results obtained when quantification is performed by using ionic Ti solutions. The applicability of the quantification method was tested on cosmetic products (moisturizing cream). Regarding validation, at the 95% confidence level, no significant differences were detected between titanium concentrations in the moisturizing cream prior sample mineralization (3865±139 mg Ti/kg sample), by FIA-ICP-MS analysis prior NPs extraction (3770±24 mg Ti/kg sample), and after using the optimized on-line calibration approach (3699±145 mg Ti/kg sample). Besides the high Ti content found in the studied food products (sugar glass and coffee cream), TiO2NPs were not detected. Copyright © 2014 Elsevier B.V. All rights reserved.

A rapid and high-precision method for sulfur isotope δ(34)S determination with a multiple-collector inductively coupled plasma mass spectrometer: matrix effect correction and applications for water samples without chemical purification.

PubMed

Lin, An-Jun; Yang, Tao; Jiang, Shao-Yong

2014-04-15

Previous studies have indicated that prior chemical purification of samples, although complex and time-consuming, is essential in obtaining precise and accurate results for sulfur isotope ratios using multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). In this study, we introduce a new, rapid and precise MC-ICP-MS method for sulfur isotope determination from water samples without chemical purification. The analytical work was performed on an MC-ICP-MS instrument with medium mass resolution (m/Δm ~ 3000). Standard-sample bracketing (SSB) was used to correct samples throughout the analytical sessions. Reference materials included an Alfa-S (ammonium sulfate) standard solution, ammonium sulfate provided by the lab of the authors and fresh seawater from the South China Sea. A range of matrix-matched Alfa-S standard solutions and ammonium sulfate solutions was used to investigate the matrix (salinity) effect (matrix was added in the form of NaCl). A seawater sample was used to confirm the reliability of the method. Using matrix-matched (salinity-matched) Alfa-S as the working standard, the measured δ(34)S value of AS (-6.73 ± 0.09‰) was consistent with the reference value (-6.78 ± 0.07‰) within the uncertainty, suggesting that this method could be recommended for the measurement of water samples without prior chemical purification. The δ(34)S value determination for the unpurified seawater also yielded excellent results (21.03 ± 0.18‰) that are consistent with the reference value (20.99‰), thus confirming the feasibility of the technique. The data and the results indicate that it is feasible to use MC-ICP-MS and matrix-matched working standards to measure the sulfur isotopic compositions of water samples directly without chemical purification. In comparison with the existing MC-ICP-MS techniques, the new method is better for directly measuring δ(34)S values in water samples with complex matrices; therefore, it can significantly accelerate analytical turnover. Copyright © 2014 John Wiley & Sons, Ltd.

A method for direct, semi-quantitative analysis of gas phase samples using gas chromatography-inductively coupled plasma-mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carter, Kimberly E; Gerdes, Kirk

2013-07-01

A new and complete GC–ICP-MS method is described for direct analysis of trace metals in a gas phase process stream. The proposed method is derived from standard analytical procedures developed for ICP-MS, which are regularly exercised in standard ICP-MS laboratories. In order to implement the method, a series of empirical factors were generated to calibrate detector response with respect to a known concentration of an internal standard analyte. Calibrated responses are ultimately used to determine the concentration of metal analytes in a gas stream using a semi-quantitative algorithm. The method was verified using a traditional gas injection from a GCmore » sampling valve and a standard gas mixture containing either a 1 ppm Xe + Kr mix with helium balance or 100 ppm Xe with helium balance. Data collected for Xe and Kr gas analytes revealed that agreement of 6–20% with the actual concentration can be expected for various experimental conditions. To demonstrate the method using a relevant “unknown” gas mixture, experiments were performed for continuous 4 and 7 hour periods using a Hg-containing sample gas that was co-introduced into the GC sample loop with the xenon gas standard. System performance and detector response to the dilute concentration of the internal standard were pre-determined, which allowed semi-quantitative evaluation of the analyte. The calculated analyte concentrations varied during the course of the 4 hour experiment, particularly during the first hour of the analysis where the actual Hg concentration was under predicted by up to 72%. Calculated concentration improved to within 30–60% for data collected after the first hour of the experiment. Similar results were seen during the 7 hour test with the deviation from the actual concentration being 11–81% during the first hour and then decreasing for the remaining period. The method detection limit (MDL) was determined for the mercury by injecting the sample gas into the system following a period of equilibration. The MDL for Hg was calculated as 6.8 μg · m -3. This work describes the first complete GC–ICP-MS method to directly analyze gas phase samples, and detailed sample calculations and comparisons to conventional ICP-MS methods are provided.« less

Inductively coupled plasma mass spectrometry (ICP MS): a versatile tool.

PubMed

Ammann, Adrian A

2007-04-01

Inductively coupled plasma (ICP) mass spectrometry (MS) is routinely used in many diverse research fields such as earth, environmental, life and forensic sciences and in food, material, chemical, semiconductor and nuclear industries. The high ion density and the high temperature in a plasma provide an ideal atomizer and element ionizer for all types of samples and matrices introduced by a variety of specialized devices. Outstanding properties such as high sensitivity (ppt-ppq), relative salt tolerance, compound-independent element response and highest quantitation accuracy lead to the unchallenged performance of ICP MS in efficiently detecting, identifying and reliably quantifying trace elements. The increasing availability of relevant reference compounds and high separation selectivity extend the molecular identification capability of ICP MS hyphenated to species-specific separation techniques. While molecular ion source MS is specialized in determining the structure of unknown molecules, ICP MS is an efficient and highly sensitive tool for target-element orientated discoveries of relevant and unknown compounds. This special-feature, tutorial article presents the principle and advantages of ICP MS, highlighting these using examples from recently published investigations. Copyright 2007 John Wiley & Sons, Ltd.

Trace Metal-Humic Complexes in Natural Waters: Insights From Speciation Experiments

NASA Astrophysics Data System (ADS)

Stern, J. C.; Salters, V.; Sonke, J.

2006-12-01

The DOM cycle is intimately linked to the cycling and bioavailability of trace metals in aqueous environments. The presence or absence of DOM in the water column can determined whether trace elements will be present in limited quantities as a nutrient, or in surplus quantities as a toxicant. Humic substances (HS), which represent the refractory products of DOM degradation, strongly affect the speciation of trace metals in natural waters. To simulate metal-HS interactions in nature, experiments must be carried out using trace metal concentrations. Sensitive detection systems such as ICP-MS make working with small (nanomolar) concentrations possible. Capillary electrophoresis coupled with ICP-MS (CE-ICP-MS) has recently been identified as a rapid and accurate method to separate metal species and calculate conditional binding constants (log K_c) of metal-humic complexes. CE-ICP-MS was used to measure partitioning of metals between humic substances and a competing ligand (EDTA) and calculate binding constants of rare earth element (REE) and Th, Hf, and Zr-humic complexes at pH 3.5-8 and ionic strength of 0.1. Equilibrium dialysis ligand exchange (EDLE) experiments to validate the CE-ICP-MS method were performed to separate the metal-HS and metal-EDTA species by partitioning due to size exclusion via diffusion through a 1000 Da membrane. CE-ICP-MS experiments were also conducted to compare binding constants of REE with humic substances of various origin, including soil, peat, and aquatic DOM. Results of our experiments show an increase in log K_c with decrease in ionic radius for REE-humic complexes (the lanthanide contraction effect). Conditional binding constants of tetravalent metal-humic complexes were found to be several orders of magnitude higher than REE-humic complexes, indicating that tetravalent metals have a very strong affinity for humic substances. Because thorium is often used as a proxy for the tetravalent actinides, Th-HS binding constants can allow us to assess the importance of tetravalent actinide-humic complexes in groundwater transport from nuclear repositories. Our results suggest that tetravalent actinide-humic complexes couild be more important to account for in predictive speciation models than previously thought.

Determination of (90)Sr in soil samples using inductively coupled plasma mass spectrometry equipped with dynamic reaction cell (ICP-DRC-MS).

PubMed

Feuerstein, J; Boulyga, S F; Galler, P; Stingeder, G; Prohaska, T

2008-11-01

A rapid method is reported for the determination of (90)Sr in contaminated soil samples in the vicinity of the Chernobyl Nuclear Power Plant by ICP-DRC-MS. Sample preparation and measurement procedures focus on overcoming the isobaric interference of (90)Zr, which is present in soils at concentrations higher by more than six orders of magnitude than (90)Sr. Zirconium was separated from strontium in two steps to reduce the interference by (90)Zr(+) ions by a factor of more than 10(7): (i) by ion exchange using a Sr-specific resin and (ii) by reaction with oxygen as reaction gas in a dynamic reaction cell (DRC) of a quadrupole ICP-MS. The relative abundance sensitivity of the ICP-MS was studied systematically and the peak tailing originating from (88)Sr on mass 90 u was found to be about 3 x 10(-9). Detection limits of 4 fg g(-1) (0.02 Bq g(-1)) were achieved when measuring Sr solutions containing no Zr. In digested uncontaminated soil samples after matrix separation as well as in a solution of 5 microg g(-1) Sr and 50 ng g(-1) Zr a detection limit of 0.2 pg g(-1) soil (1 Bq g(-1) soil) was determined. (90)Sr concentrations in three soil samples collected in the vicinity of the Chernobyl Nuclear Power Plant were 4.66+/-0.27, 13.48+/-0.68 and 12.9+/-1.5 pg g(-1) corresponding to specific activities of 23.7+/-1.3, 68.6+/-3.5 and 65.6+/-7.8 Bq g(-1), respectively. The ICP-DRC-MS results were compared to the activities measured earlier by radiometry. Although the ICP-DRC-MS is inferior to commonly used radiometric methods with respect to the achievable minimum detectable activity it represents a time- and cost-effective alternative technique for fast monitoring of high-level (90)Sr contamination in environmental or nuclear industrial samples down to activities of about 1 Bq g(-1).

Determination of 99Tc in fresh water using TRU resin by ICP-MS.

PubMed

Guérin, Nicolas; Riopel, Remi; Kramer-Tremblay, Sheila; de Silva, Nimal; Cornett, Jack; Dai, Xiongxin

2017-10-02

Technetium-99 ( 99 Tc) determination at trace level by inductively coupled plasma mass spectrometry (ICP-MS) is challenging because there is no readily available appropriate Tc isotopic tracer. A new method using Re as a recovery tracer to determine 99 Tc in fresh water samples, which does not require any evaporation step, was developed. Tc(VII) and Re(VII) were pre-concentrated on a small anion exchange resin (AER) cartridge from one litre of water sample. They were then efficiently eluted from the AER using a potassium permanganate (KMnO 4 ) solution. After the reduction of KMnO 4 in 2 M sulfuric acid solution, the sample was passed through a small TRU resin cartridge. Tc(VII) and Re(VII) retained on the TRU resin were eluted using near boiling water, which can be directly used for the ICP-MS measurement. The results for method optimisation, validation and application were reported. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

Trace-Level Automated Mercury Speciation Analysis

PubMed Central

Taylor, Vivien F.; Carter, Annie; Davies, Colin; Jackson, Brian P.

2011-01-01

An automated system for methyl Hg analysis by purge and trap gas chromatography (GC) was evaluated, with comparison of several different instrument configurations including chromatography columns (packed column or capillary), detector (atomic fluorescence, AFS, or inductively coupled plasma mass spectrometry, ICP-MS, using quadrupole and sector field ICP- MS instruments). Method detection limits (MDL) of 0.042 pg and 0.030 pg for CH3Hg+ were achieved with the automated Hg analysis system configured with AFS and ICPMS detection, respectively. Capillary GC with temperature programming was effective in improving resolution and decreasing retention times of heavier Hg species (in this case C3H7Hg+) although carryover between samples was increased. With capillary GC, the MDL for CH3Hg+ was 0.25 pg for AFS detection and 0.060 pg for ICP-MS detection. The automated system was demonstrated to have high throughput (72 samples analyzed in 8 hours) requiring considerably less analyst time than the manual method for methyl mercury analysis described in EPA 1630. PMID:21572543

A candidate reference method for serum potassium measurement by inductively coupled plasma mass spectrometry.

PubMed

Yan, Ying; Han, Bingqing; Zeng, Jie; Zhou, Weiyan; Zhang, Tianjiao; Zhang, Jiangtao; Chen, Wenxiang; Zhang, Chuanbao

2017-08-28

Potassium is an important serum ion that is frequently assayed in clinical laboratories. Quality assurance requires reference methods; thus, the establishment of a candidate reference method for serum potassium measurements is important. An inductively coupled plasma mass spectrometry (ICP-MS) method was developed. Serum samples were gravimetrically spiked with an aluminum internal standard, digested with 69% ultrapure nitric acid, and diluted to the required concentration. The 39K/27Al ratios were measured by ICP-MS in hydrogen mode. The method was calibrated using 5% nitric acid matrix calibrators, and the calibration function was established using the bracketing method. The correlation coefficients between the measured 39K/27Al ratios and the analyte concentration ratios were >0.9999. The coefficients of variation were 0.40%, 0.68%, and 0.22% for the three serum samples, and the analytical recovery was 99.8%. The accuracy of the measurement was also verified by measuring certified reference materials, SRM909b and SRM956b. Comparison with the ion selective electrode routine method and international inter-laboratory comparisons gave satisfied results. The new ICP-MS method is specific, precise, simple, and low-cost, and it may be used as a candidate reference method for standardizing serum potassium measurements.

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

NASA Astrophysics Data System (ADS)

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

2006-08-01

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

Automation of sample processing for ICP-MS determination of 90Sr radionuclide at ppq level for nuclear technology and environmental purposes.

PubMed

Kołacińska, Kamila; Chajduk, Ewelina; Dudek, Jakub; Samczyński, Zbigniew; Łokas, Edyta; Bojanowska-Czajka, Anna; Trojanowicz, Marek

2017-07-01

90 Sr is a widely determined radionuclide for environmental purposes, nuclear waste control, and can be also monitored in coolants in nuclear reactor plants. In the developed method, the ICP-MS detection was employed together with sample processing in sequential injection analysis (SIA) setup, equipped with a lab-on-valve with mechanized renewal of sorbent bed for solid-phase extraction. The optimized conditions of determination included preconcentration of 90 Sr on cation-exchange column and removal of different type of interferences using extraction Sr-resin. The limit of detection of the developed procedure depends essentially on the configuration of the employed ICP-MS spectrometer and on the available volume of the sample to be analyzed. For 1L initial sample volume, the method detection limit (MDL) value was evaluated as 2.9ppq (14.5BqL -1 ). The developed method was applied to analyze spiked river water samples, water reference materials, and also simulated and real samples of the nuclear reactor coolant. Copyright © 2016 Elsevier B.V. All rights reserved.

[Determination of iodine and its species in plant samples using ion chromatography-inductively coupled plasma mass spectrometry].

PubMed

Lin, Li; Chen, Guang; Chen, Yuhong

2011-07-01

A method was established for the determination of iodine and its species in plant samples using ion chromatography-inductively coupled plasma mass spectrometry (IC-ICP/ MS). Alkaline extraction and IC-ICP/MS were applied as the sample pre-treatment method and the detection technique respectively, for iodate and iodide determination. Moreover, high-temperature pyrolysis absorption was adopted as the pre-treatment method for total iodine analysis, which finally converted all the iodine species into iodide and measured the iodide by IC-ICP/MS. The recoveries of iodine for alkaline extraction and high-temperature pyrolysis absorption were 89.6%-97.5% and 95.2%-111.2%, respectively. The results were satisfactory. The detection limit of iodine was 0.010 mg/kg. The iodine and its speciation contents in several kinds of plant samples such as seaweeds, kelp, cabbage, tea leaf and spinach were investigated. It was shown that the iodine in seaweeds mainly existed as organic iodine; while the ones in kelp, cabbage, tea leaf and spinach mainly existed as inorganic iodine.

ICP-MS as a novel detection system for quantitative element-tagged immunoassay of hidden peanut allergens in foods.

PubMed

Careri, Maria; Elviri, Lisa; Mangia, Alessandro; Mucchino, Claudio

2007-03-01

A novel ICP-MS-based ELISA immunoassay via element-tagged determination was devised for quantitative analysis of hidden allergens in food. The method was able to detect low amounts of peanuts (down to approximately 2 mg peanuts kg(-1) cereal-based matrix) by using a europium-tagged antibody. Selectivity was proved by the lack of detectable cross-reaction with a number of protein-rich raw materials.

An Evaluation of Unit and ½ Mass Correction Approaches as a Means of Minimizing the False Positives Produced by M+2 species in US EPA Method 200.8 using ICP-MS (webinar presentation)

EPA Science Inventory

Rare earth elements (REE) and certain alkaline earths can produce M+2 interferences in ICP-MS because they have sufficiently low second ionization energies. Four REEs (150Sm, 150Nd, 156Gd and 156Dy) produce false positives on 75As and 78Se and 132Ba can produce a false positive ...

Comparative evaluation of ICP sample introduction systems to be used in the metabolite profiling of chlorine-containing pharmaceuticals via HPLC-ICP-MS.

PubMed

Klencsár, Balázs; Sánchez, Carlos; Balcaen, Lieve; Todolí, José; Lynen, Frederic; Vanhaecke, Frank

2018-05-10

A systematic evaluation of four different ICP sample introduction systems to be used in the context of metabolite profiling of chlorine-containing pharmaceuticals via HPLC-ICP-MS was carried out using diclofenac and its major metabolite, 4'-hydroxy-diclofenac, as model compounds. The strict requirements for GMP validation of chromatographic methods in the pharmaceutical industry were adhered to in this context. The final aim of this investigation is an extension of the applicability and validatability of HPLC-ICP-MS in the field of pharmaceutical R&D. Five different gradient programmes were tested while the baseline peak width (w b ), peak capacity (P), USP tailing factor (A s ) and USP signal-to-noise ratio (USP S/N) were determined as major indicators of the chromatographic performance and the values obtained were compared to the corresponding FDA recommendations (if applicable). Four different ICP-MS sample introductions systems were investigated involving two units typically working at higher flow rates (∼1.0 mL min -1 ) and another two systems working at lower flow rates (∼0.1 mL min -1 ). Optimal conditions with potential for applicability under GMP conditions were found at a mobile phase flow rate of 1.0 mL min -1 by using a pneumatic micro-flow LC nebulizer mounted onto a Peltier-cooled cyclonic spray chamber cooled to -1 °C for sample introduction. Under these conditions, HPLC-ICP-MS provided a chromatographic performance similar to that of HPLC with UV detection. The peak shape (USP tailing factor = 1.1-1.4) was significantly improved compared to that obtained with the Peltier-cooled Scott-type spray chamber. Two alternative sample introduction systems - a POINT ® and a High-Temperature Torch-Integrated Sample Introduction System (hTISIS) - were also tested at a flow rate of 0.1 mL min -1 using a chromatographic column with 1.0 mm ID. Although these systems allowed the peak shape to be improved compared to that obtained with the traditional Scott-type spray chamber, the limits of detection and of quantification achievable were strongly compromised due to the significantly lower sensitivity observed for Cl. In addition to a comparison of the aforementioned sample introduction systems, also the effect of spray chamber temperature was evaluated and it was demonstrated that proper temperature control plays an essential role in the optimization of HPLC-ICP-MS methods. Copyright © 2018 Elsevier B.V. All rights reserved.

Ultra-sensitive speciation analysis of mercury by CE-ICP-MS together with field-amplified sample stacking injection and dispersive solid-phase extraction.

PubMed

Chen, YiQuan; Cheng, Xian; Mo, Fan; Huang, LiMei; Wu, Zujian; Wu, Yongning; Xu, LiangJun; Fu, FengFu

2016-04-01

A simple dispersive solid-phase extraction (DSPE) used to extract and preconcentrate ultra-trace MeHg, EtHg and Hg(2+) from water sample, and a sensitive method for the simultaneous analysis of MeHg, EtHg and Hg(2+) by using capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS) with field-amplified sample stacking injection (FASI) were first reported in this study. The DSPE used thiol cotton particles as adsorbent, and is simple and effective. It can be used to extract and preconcentrate ultra-trace mercury compounds in water samples within 30 min with a satisfied recovery and no mercury species alteration during the process. The FASI enhanced the sensitivity of CE-ICP-MS with 25-fold, 29-fold and 27-fold for MeHg, EtHg and Hg(2+) , respectively. Using FASI-CE-ICP-MS together with DSPE, we have successfully determined ultra-trace MeHg, EtHg and Hg(2+) in tap water with a limits of quantification (LOQs) of 0.26-0.45 pg/mL, an RSD (n = 3) < 6% and a recovery of 92-108%. Ultra-high sensitivity, as well as much less sample and reagent consumption and low operating cost, make our method a valuable technique to the speciation analysis of ultra-trace mercury. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Identification of platinum nanoparticles in road dust leachate by single particle inductively coupled plasma-mass spectrometry.

PubMed

Folens, Karel; Van Acker, Thibaut; Bolea-Fernandez, Eduardo; Cornelis, Geert; Vanhaecke, Frank; Du Laing, Gijs; Rauch, Sebastien

2018-02-15

Elevated platinum (Pt) concentrations are found in road dust as a result of emissions from catalytic converters in vehicles. This study investigates the occurrence of Pt in road dust collected in Ghent (Belgium) and Gothenburg (Sweden). Total Pt contents, determined by tandem ICP-mass spectrometry (ICP-MS/MS), were in the range of 5 to 79ngg -1 , comparable to the Pt content in road dust of other medium-sized cities. Further sample characterization was performed by single particle (sp) ICP-MS following an ultrasonic extraction procedure using stormwater runoff for leaching. The method was found to be suitable for the characterization of Pt nanoparticles in road dust leachates. The extraction was optimized using road dust reference material BCR-723, for which an extraction efficiency of 2.7% was obtained by applying 144kJ of ultrasonic energy. Using this method, between 0.2% and 18% of the Pt present was extracted from road dust samples. spICP-MS analysis revealed that Pt in the leachate is entirely present as nanoparticles of sizes between 9 and 21nm. Although representing only a minor fraction of the total content in road dust, the nanoparticulate Pt leachate is most susceptible to biological uptake and hence most relevant in terms of bioavailability. Copyright © 2017 Elsevier B.V. All rights reserved.

Northwest Africa 5298: A Basaltic Shergottite

NASA Technical Reports Server (NTRS)

Hui, Hejiu; Peslier, Anne; Lapen, Thomas J.; Brandon, Alan; Shafer, John

2009-01-01

NWA 5298 is a single 445 g meteorite found near Bir Gandouz, Morocco in March 2008 [1]. This rock has a brown exterior weathered surface instead of a fusion crust and the interior is composed of green mineral grains with interstitial dark patches containing small vesicles and shock melts [1]. This meteorite is classified as a basaltic shergottite [2]. A petrologic study of this Martian meteorite is being carried out with electron microprobe analysis and soon trace element analyses by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Oxygen fugacity is calculated from Fe-Ti oxides pairs in the sample. The data from this study constrains the petrogenesis of basaltic shergottites.

Determination of impurities in uranium matrices by time-of-flight ICP-MS using matrix-matched method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buerger, Stefan; Riciputi, Lee R; Bostick, Debra A

2007-01-01

The analysis of impurities in uranium matrices is performed in a variety of fields, e.g. for quality control in the production stream converting uranium ores to fuels, as element signatures in nuclear forensics and safeguards, and for non-proliferation control. We have investigated the capabilities of time-of-flight ICP-MS for the analysis of impurities in uranium matrices using a matrix-matched method. The method was applied to the New Brunswick Laboratory CRM 124(1-7) series. For the seven certified reference materials, an overall precision and accuracy of approximately 5% and 14%, respectively, were obtained for 18 analyzed elements.

Determination of serum calcium levels by 42Ca isotope dilution inductively coupled plasma mass spectrometry.

PubMed

Han, Bingqing; Ge, Menglei; Zhao, Haijian; Yan, Ying; Zeng, Jie; Zhang, Tianjiao; Zhou, Weiyan; Zhang, Jiangtao; Wang, Jing; Zhang, Chuanbao

2017-11-27

Serum calcium level is an important clinical index that reflects pathophysiological states. However, detection accuracy in laboratory tests is not ideal; as such, a high accuracy method is needed. We developed a reference method for measuring serum calcium levels by isotope dilution inductively coupled plasma mass spectrometry (ID ICP-MS), using 42Ca as the enriched isotope. Serum was digested with 69% ultrapure nitric acid and diluted to a suitable concentration. The 44Ca/42Ca ratio was detected in H2 mode; spike concentration was calibrated by reverse IDMS using standard reference material (SRM) 3109a, and sample concentration was measured by a bracketing procedure. We compared the performance of ID ICP-MS with those of three other reference methods in China using the same serum and aqueous samples. The relative expanded uncertainty of the sample concentration was 0.414% (k=2). The range of repeatability (within-run imprecision), intermediate imprecision (between-run imprecision), and intra-laboratory imprecision were 0.12%-0.19%, 0.07%-0.09%, and 0.16%-0.17%, respectively, for two of the serum samples. SRM909bI, SRM909bII, SRM909c, and GBW09152 were found to be within the certified value interval, with mean relative bias values of 0.29%, -0.02%, 0.10%, and -0.19%, respectively. The range of recovery was 99.87%-100.37%. Results obtained by ID ICP-MS showed a better accuracy than and were highly correlated with those of other reference methods. ID ICP-MS is a simple and accurate candidate reference method for serum calcium measurement and can be used to establish and improve serum calcium reference system in China.

Rapid Analysis of the Size Distribution of Metal-Containing Aerosol

PubMed Central

Park, Jae Hong; Mudunkotuwa, Imali A.; Crawford, Kathryn J.; Anthony, T. Renée; Grassian, Vicki H.; Peters, Thomas M.

2017-01-01

Conventional methods to measure the metallic content of particles by size are time consuming and expensive, requiring collection of particles with a cascade impactor and subsequent metals analysis by inductively coupled plasma mass spectrometry (ICP-MS). In this work, we describe a rapid way to measure the size distribution of metal-containing particles from 10 nm to 20 μm, using a nano micro-orifice uniform-deposit impactor (nano-MOUDI) to size-selective and collect particles that are then analyzed with a field portable X-ray fluorescence (FP-XRF) to determine metal composition and concentration. The nano-MOUDI was used to sample a stainless-steel aerosol produced by a spark discharge system. The particle-laden substrates were then analyzed directly with FP-XRF and then with ICP-MS. Results from FP-XRF were linearly correlated with results from ICP-MS (R2 = 0.91 for Fe and R2 = 0.84 for Cr). Although the FP-XRF was unable to detect Fe particles at mass per substrate loadings less than 2.5 μg effectively, it produced results similar to those using the ICP-MS at a mass per substrate loading greater than 2.5 μg. PMID:28871214

Validation of Electrochemically Modulated Separations Performed On-Line with MC-ICP-MS for Uranium and Plutonium Isotopic Analyses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liezers, Martin; Olsen, Khris B.; Mitroshkov, Alexandre V.

2010-08-11

The most time consuming process in uranium or plutonium isotopic analyses is performing the requisite chromatographic separation of the actinides. Filament preparation for thermal ionization (TIMS) adds further delays, but is generally accepted due to the unmatched performance in trace isotopic analyses. Advances in Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS) are beginning to rival the performance of TIMS. Methods, such as Electrochemically Modulated Separations (EMS) can efficiently pre-concentrate U or Pu quite selectively from small solution volumes in a matrix of 0.5 M nitric acid. When performed in-line with ICP-MS, the rapid analyte release from the electrode is fast,more » and large transient analyte signal enhancements of >100 fold can be achieved as compared to more conventional continuous nebulization of the original starting solution. This makes the approach ideal for very low level isotope ratio measurements. In this paper, some aspects of EMS performance are described. These include low level Pu isotope ratio behavior versus concentration by MC-ICP-MS and uranium rejection characteristics that are also important for reliable low level Pu isotope ratio determinations.« less

Stable isotope labelling methods in mass spectrometry-based quantitative proteomics.

PubMed

Chahrour, Osama; Cobice, Diego; Malone, John

2015-09-10

Mass-spectrometry based proteomics has evolved as a promising technology over the last decade and is undergoing a dramatic development in a number of different areas, such as; mass spectrometric instrumentation, peptide identification algorithms and bioinformatic computational data analysis. The improved methodology allows quantitative measurement of relative or absolute protein amounts, which is essential for gaining insights into their functions and dynamics in biological systems. Several different strategies involving stable isotopes label (ICAT, ICPL, IDBEST, iTRAQ, TMT, IPTL, SILAC), label-free statistical assessment approaches (MRM, SWATH) and absolute quantification methods (AQUA) are possible, each having specific strengths and weaknesses. Inductively coupled plasma mass spectrometry (ICP-MS), which is still widely recognised as elemental detector, has recently emerged as a complementary technique to the previous methods. The new application area for ICP-MS is targeting the fast growing field of proteomics related research, allowing absolute protein quantification using suitable elemental based tags. This document describes the different stable isotope labelling methods which incorporate metabolic labelling in live cells, ICP-MS based detection and post-harvest chemical label tagging for protein quantification, in addition to summarising their pros and cons. Copyright © 2015 Elsevier B.V. All rights reserved.

Slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry for the determination of Cr, Cd and Pb in plastics.

PubMed

Li, Po-Chien; Jiang, Shiuh-Jen

2006-07-01

Ultrasonic slurry sampling electrothermal vaporization dynamic reaction cell inductively coupled plasma mass spectrometry (USS-ETV-DRC-ICP-MS) for the determination of Cr, Cd and Pb in several plastic samples, using NH4NO3 as the modifier, is described. The influences of the instrumental operating conditions and the slurry preparation technique on the ion signals are investigated. A reduction in the intensity of the background at signals corresponding to chromium masses (arising from matrix elements) was achieved by using NH3 as the reaction cell gas in the DRC. The method was applied to determine Cr, Cd and Pb in two polystyrene (PS) samples and a polyvinyl chloride (PVC) sample using two different calibration methods, namely standard addition and isotope dilution. The results were in good agreement with those for digested samples analyzed by ultrasonic nebulization DRC-ICP-MS. The precision between sample replicates was better than 17% with the USS-ETV-DRC-ICP-MS method. The method detection limits, estimated from standard addition curves, were about 6-9, 1-2 and 8-11 ng g(-1) for Cr, Cd and Pb, respectively, in the original plastic samples.

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

PubMed

Chahrour, Osama; Malone, John

2017-01-01

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

Detection and characterisation of aluminium-containing nanoparticles in Chinese noodles by single particle ICP-MS.

PubMed

Loeschner, Katrin; Correia, Manuel; López Chaves, Carlos; Rokkjær, Inge; Sloth, Jens J

2018-01-01

This study investigated Chinese noodles for the presence of aluminium-containing nanoparticles by using inductively coupled plasma mass spectrometry in single particle mode (spICP-MS) after enzymatic digestion by α-amylase. The aluminium concentrations in the noodle samples, determined by conventional ICP-MS without or with the use of hydrofluoric acid for digestion, were 5.4 ± 1.9 µg/g and 10.1 ± 2.2 µg/g (N = 21), respectively. Aluminium-containing nanoparticles were detected by spICP-MS in all 21 samples. Depending on the assumed particle composition, Al 2 O 3 or Al 2 O 3 ∙2SiO 2 ∙2H 2 O, the median particle diameters were either below or above 100 nm, respectively. The minimum detectable particle diameter by spICP-MS was between 54 and 83 nm. The mass recovery of aluminium in the form of particles was between 5% and 18%. The presented work reports for the first time the detection of Al-containing particles in food by spICP-MS.

The performance of single and multi-collector ICP-MS instruments for fast and reliable 34S/32S isotope ratio measurements†

PubMed Central

Pröfrock, Daniel; Irrgeher, Johanna; Prohaska, Thomas

2016-01-01

The performance and validation characteristics of different single collector inductively coupled plasma mass spectrometers based on different technical principles (ICP-SFMS, ICP-QMS in reaction and collision modes, and ICP-MS/MS) were evaluated in comparison to the performance of MC ICP-MS for fast and reliable S isotope ratio measurements. The validation included the determination of LOD, BEC, measurement repeatability, within-lab reproducibility and deviation from certified values as well as a study on instrumental isotopic fractionation (IIF) and the calculation of the combined standard measurement uncertainty. Different approaches of correction for IIF applying external intra-elemental IIF correction (aka standard-sample bracketing) using certified S reference materials and internal inter-elemental IIF (aka internal standardization) correction using Si isotope ratios in MC ICP-MS are explained and compared. The resulting combined standard uncertainties of examined ICP-QMS systems were not better than 0.3–0.5% (uc,rel), which is in general insufficient to differentiate natural S isotope variations. Although the performance of the single collector ICP-SFMS is better (single measurement uc,rel = 0.08%), the measurement reproducibility (>0.2%) is the major limit of this system and leaves room for improvement. MC ICP-MS operated in the edge mass resolution mode, applying bracketing for correction of IIF, provided isotope ratio values with the highest quality (relative combined measurement uncertainty: 0.02%; deviation from the certified value: <0.002%). PMID:27812369

The performance of single and multi-collector ICP-MS instruments for fast and reliable 34S/32S isotope ratio measurements.

PubMed

Hanousek, Ondrej; Brunner, Marion; Pröfrock, Daniel; Irrgeher, Johanna; Prohaska, Thomas

2016-11-14

The performance and validation characteristics of different single collector inductively coupled plasma mass spectrometers based on different technical principles (ICP-SFMS, ICP-QMS in reaction and collision modes, and ICP-MS/MS) were evaluated in comparison to the performance of MC ICP-MS for fast and reliable S isotope ratio measurements. The validation included the determination of LOD, BEC, measurement repeatability, within-lab reproducibility and deviation from certified values as well as a study on instrumental isotopic fractionation (IIF) and the calculation of the combined standard measurement uncertainty. Different approaches of correction for IIF applying external intra-elemental IIF correction (aka standard-sample bracketing) using certified S reference materials and internal inter-elemental IIF (aka internal standardization) correction using Si isotope ratios in MC ICP-MS are explained and compared. The resulting combined standard uncertainties of examined ICP-QMS systems were not better than 0.3-0.5% ( u c,rel ), which is in general insufficient to differentiate natural S isotope variations. Although the performance of the single collector ICP-SFMS is better (single measurement u c,rel = 0.08%), the measurement reproducibility (>0.2%) is the major limit of this system and leaves room for improvement. MC ICP-MS operated in the edge mass resolution mode, applying bracketing for correction of IIF, provided isotope ratio values with the highest quality (relative combined measurement uncertainty: 0.02%; deviation from the certified value: <0.002%).

Morphology and structure of TixOy nanoparticles generated by femtosecond laser ablation in water

NASA Astrophysics Data System (ADS)

Donėlienė, Jolanta; Rudzikas, Matas; Rades, Steffi; Dörfel, Ilona; Peplinski, Burkhard; Sahre, Mario; Pellegrino, Francesco; Maurino, Valter; Ulbikas, Juras; Galdikas, Algirdas; Hodoroaba, Vasile-Dan

2018-04-01

In this work femto-second pulsed laser ablation in liquid (PLAL) procedure for the generation of titanium oxide nanoparticles (NP) is reported with the purpose of understanding morphology and structure of the newly generated NPs. Ablation duration was varied for optimization of NP generation processes between 10 and 90 min. Surface morphology of NPs as well as their size and shape (distribution) were analysed by various complementary electron microscopy techniques, i.e. SEM, TSEM and TEM. The crystalline structure of titanium oxide particles was investigated by XRD (two instruments operated in different geometries) and HR-TEM. Concentration of generated titanium oxide NPs in liquid was analysed by ICP-MS. A mix of crystalline (mainly anatase), partly crystalline and amorphous spherical titanium oxide NPs can be reported having a mean size between 10 and 20 nm, which is rather independent of the laser ablation (LA) duration. A second component consisting of irregularly shaped, but crystalline titanium oxide nanostructures is co-generated in the LA water, with more pronounced occurrence at longer LA times. The provenance of this component is assigned to those spherical particles generated in suspension and passing through the converging laser beam, being hence subject to secondary irradiation effects, e. g. fragmentation.

Multi-elemental bio-imaging of rat tissue from a study investigating the bioavailability of bismuth from shotgun pellets.

PubMed

Urgast, Dagmar S; Ellingsen, Dag G; Berlinger, Balázs; Eilertsen, Einar; Friisk, Grete; Skaug, Vidar; Thomassen, Yngvar; Beattie, John H; Kwun, In-Sook; Feldmann, Jörg

2012-07-01

In recent years, bismuth has been promoted as a "green element" and is used as a substitute for the toxic lead in ammunition and other applications. However, the bioavailability and toxicity of bismuth is still not very well described. Following a hunting accident with bismuth-containing shots, a bioavailability study of bismuth from metal pellets inoculated into rat limb muscles was carried out. Bismuth could be found in urine and blood of the animals. Bio-imaging using laser ablation ICP-MS of thin sections of the tissue around the metal implant was carried out to find out more about the distribution of the metal diffusing into the tissue. Two laser ablation systems with different ablation cell designs were compared regarding their analytical performance. Low concentrations of bismuth showing a non-symmetrical pattern were detected in the tissue surrounding the metal implant. This was partly an artefact from cutting the thin sections but also bio-mobilisation of the metals of the implant could be seen. An accumulation of zinc around the implant was interpreted as a marker of inflammation. Challenges regarding sample preparation for laser ablation and bio-imaging of samples of diverse composition became apparent during the analysis.

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

PubMed

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

2016-05-30

A fast, accurate and precise method for the separation and determination of the total contents of drug-related Cl and Br in human blood plasma, based on high performance liquid chromatography - inductively coupled plasma - tandem mass spectrometry (HPLC-ICP-MS/MS), has been developed. The novel approach was proved to be a suitable alternative to the presently used standard methodology (i.e. based on a radiolabelled version of the drug molecule and radiodetection), while eliminating the disadvantages of the latter. Interference-free determination of (35)Cl has been accomplished via ICP-MS/MS using H2 as reaction gas and monitoring the (35)ClH2(+) reaction product at mass-to-charge ratio of 37. Br could be measured "on mass" at a mass-to-charge of 79. HPLC was relied on for the separation of the drug-related entities from the substantial amount of inorganic Cl. The method developed was found to be sufficiently precise (repeatability <10% RSD) and accurate (recovery between 95 and 105%) and shows a linear dynamic range (R(2)>0.990) from the limit of quantification (0.05 and 0.01 mg/L for Cl and Br in blood plasma, respectively) to at least 5 and 1mg/L for Cl and Br, respectively. Quantification via either external or internal standard calibration provides reliable results for both elements. As a proof-of-concept, human blood plasma samples from a clinical study involving a newly developed Cl- and Br-containing active pharmaceutical ingredient were analysed and the total drug exposure was successfully described. Cross-validation was achieved by comparing the results obtained on Cl- and on Br-basis. Copyright © 2016 Elsevier B.V. All rights reserved.

Single particle analysis of TiO2 in candy products using triple quadrupole ICP-MS.

PubMed

Candás-Zapico, S; Kutscher, D J; Montes-Bayón, M; Bettmer, J

2018-04-01

Titanium dioxide (TiO 2 ) belongs to the materials that have gained great importance in many applications. In its particulate form (micro- or nanoparticles), it has entered a huge number of consumer products and food-grade TiO 2 , better known as E171 within the European Union, represents an important food additive. Thus, there is an increasing need for analytical methods able to detect and quantify such particles. In this regard, inductively coupled-mass spectrometry (ICP-MS), in particular single particle ICP-MS (spICP-MS), has gained importance due to its simplicity and ease of use. Nevertheless, the number of applications for Ti nanoparticles is rather limited. In this study, we have applied the spICP-MS strategy by comparing different measuring modes available in triple quadrupole ICP-MS. First, single quadrupole mode using the collision/reaction cell system was selected for monitoring the isotope 47 Ti. Different cell gases like He, O 2 and NH 3 were tested under optimised conditions for its applicability in spICP-MS of standard suspensions of TiO 2 . The determined analytical figures of merit were compared to those obtained by triple quadrupole mode using the 47 Ti or 48 Ti reaction products using O 2 and NH 3 as reaction gases. This comparison demonstrated that the triple quadrupole mode (TQ mode) was superior in terms of sensitivity due to the more efficient removal of spectral interferences. Particle size detection limits down to 26nm were obtained using the best instrumental conditions for TiO 2 particles at a dwell time of 10ms. Finally, the different measuring modes were applied to the analysis of chewing gum samples after a simple extraction procedure using an ultrasonic bath. The obtained results showed a good agreement for the detected particle size range using the different TQ modes. The size range of TiO 2 particles was determined to be between approximately 30 and 200nm, whereas roughly 40% of the particles were smaller than 100nm. For the determination of the particle number concentration in these real samples, we suggest CeO 2 particles as internal standard. Copyright © 2017 Elsevier B.V. All rights reserved.

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

2014-12-03

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. Copyright © 2014 Elsevier B.V. All rights reserved.

The Contrast in Outgassing of Germanium Between Shergottites and Nakhlites

NASA Technical Reports Server (NTRS)

Yang, S.; Humayun, M.; Righter, K.; Peslier, A. H.

2018-01-01

Final Paper and not the abstract is attached. Introduction: Germanium is generally thought to follow Si in its geochemical behavior, but little data has existed to rigorously understand the behavior of Ge in the Martian mantle. Germanium is known to be more siderophile than Si, and its partitioning into the martian core has been studied by. Typical abundances in igneous martian meteorites range from 0.5-3 ppm, a larger range than what is observed in terrestrial basalts (1.5 +/- 0.1 ppm). In situ measurements by the MER and MSL rovers have revealed a surprisingly large range in Ge abundances in surface rocks (30-650 ppm), but many igneous rocks and soils are shown to have greater than 30 ppm Ge (the detection limit of the APXS). Recently, reported that shergottite minerals showed a depletion of Ge with increasing fractionation, while nakhlites and chassignites exhibited Ge behavior compatible with closed system igneous differentiation. They interpreted their observations as tentatively indicating volcanic outgassing of Ge from shergottites (but not from nakhlite-chassignites) with recondensation of the Ge vapor into soils and breccias. Recent experimental studies show that Ge is significantly volatile from magmas. In this study, we followed up on those results by analyzing minerals in five nakhlites and five shergottites by laser ablation ICP-MS (LA-ICP-MS). See Attached

Evaluation of a tunable bandpass reaction cell inductively coupled plasma mass spectrometer for the determination of selenium in serum and urine

NASA Astrophysics Data System (ADS)

Nixon, David E.; Neubauer, Kenneth R.; Eckdahl, Steven J.; Butz, John A.; Burritt, Mary F.

2003-01-01

A Dynamic Reaction Cell™ inductively coupled plasma mass spectrometer (DRC-ICP-MS) was evaluated for the determination of selenium in serum and urine. Reaction cell conditions were evaluated for the suppression of Ar 2+ dimer at m/ z 78 and 80 using methane as the reaction gas. A diluent containing 10% ethanol, 1% nitric acid, 0.5% Triton X-100 with gallium and yttrium internal standards was used to dilute urine and serum samples. Instrument response calibration was achieved by using aqueous acidic standards spiked into a urine matrix. Slopes for aqueous inorganic selenium, seleno- DL-cystine, seleno- DL-methionine and trimethylselenonium iodide spiked into urine and serum matrices were nearly identical. In general, reagent blank readings and detection limits were significantly lower in the DRC mode (reaction cell pressurized) than the standard mode (cell vented). Average results for the analysis of National Institute of Standards and Technology Standard Reference Material (NIST SRM) 1598 bovine serum (attained over 13 days) are: 43.8±3.6 μg Se/l. Reference concentration is 43.6±3.6 μg Se/l. For NIST SRM 2670 Normal Urine the DRC-ICP-MS results are 30.7±4.6 μg Se/l with a certified concentration of 30±8 μg Se/l. For NIST SRM 2670 Elevated Urine the DRC-ICP-MS results are 463±35 μg Se/l with a certified concentration of 460±30 μg Se/l. The DRC-ICP-MS results for selenium determinations in urine and serum survey samples from the Institut National de Sante Publique du Quebec were compared with the reference concentrations and results produced by conventional ICP-MS. While conventional ICP-MS gave acceptable results for survey samples, DRC-ICP-MS gave excellent results for both urine and sera. Closer correlation was observed for DRC-ICP-MS results with target concentrations than with conventional ICP-MS.

Direct lead isotope analysis in Hg-rich sulfides by LA-MC-ICP-MS with a gas exchange device and matrix-matched calibration.

PubMed

Zhang, Wen; Hu, Zhaochu; Günther, Detlef; Liu, Yongsheng; Ling, Wenli; Zong, Keqing; Chen, Haihong; Gao, Shan

2016-12-15

In situ Pb isotope data of sulfide samples measured by LA-MC-ICP-MS provide valuable geochemical information for studies of the origin and evolution of ore deposits. However, the severe isobaric interference of 204 Hg on 204 Pb and the lack of matrix-matched sulfide reference materials limit the precision of Pb isotopic analyses for Hg-rich sulfides. In this study, we observe that Hg forms vapor and can be completely removed from sample aerosol particles produced by laser ablation using a gas exchange device. Additionally, this device does not influence the signal intensities of Pb isotopes. The within-run precision, the external reproducibility and the analytical accuracy are significantly improved for the Hg-rich sulfide samples using this mercury-vapor-removing device. Matrix effects are observed when using silicate glass reference materials as the external standards to assess the relationship of mass fractionation factors between Tl and Pb in sulfide samples, resulting in a maximum deviation of ∼0.20% for 20x Pb/ 204 Pb. Matrix-matched reference materials are therefore required for the highly precise and accurate Pb isotope analyses of sulfide samples. We investigated two sulfide samples, MASS-1 (the Unites States Geological Survey reference materials) and Sph-HYLM (a natural sphalerite), as potential candidates. Repeated analyses of the two proposed sulfide reference materials by LA-MC-ICP-MS yield good external reproducibility of <0.04% (RSD, k = 2) for 20x Pb/ 206 Pb and <0.06% (RSD, k = 2) for 20x Pb/ 204 Pb with the exception of 20x Pb/ 204 Pb in MASS-1, which provided an external reproducibility of 0.24% (RSD, k = 2). Because the concentration of Pb in MASS-1 (76 μg g -1 ) is ∼5.2 times lower than that in Sph-HYLM (394 ± 264 μg g -1 ). The in situ analytical results of MASS-1 and Sph-HYLM are consistent with the values obtained by solution MC-ICP-MS, demonstrating the reliability and robustness of our analytical protocol. Copyright © 2016 Elsevier B.V. All rights reserved.

Neodymium Isotopic Compositions of the Titanite Reference Materials Used in U-Pb Geochronology

NASA Astrophysics Data System (ADS)

Ma, Q.; Yang, Y.; Zhao, Z.

2017-12-01

Titanite (CaTiSiO5) is a widespread mineral and preferentially incorporates considerable uranium and significant light rare earth elements (LREEs) in its structure. Geochronology based upon U-Pb and Pb-Pb analyses of titanite has proven to be useful for understanding the P-T-t evolution of many igneous, metamorphic and hydrothermally altered rock samples (Scott and St-Onge, 1995). In the meantime, Sm-Nd isotopic composition in single titanite can be used to obtain initial Nd isotope composition at the time of titanite crystallization when combined with its U-Pb age, making titanite the most versatile mineral for dating metamorphism and tracing hydrothermal source (Amelin et al., 2009). The widely utilized in situ analyses by SIMS and LA-(MC)-ICP-MS have emphasized the significance for uniform and homogeneous reference materials for external correction (Liu et al., 2012, Sun et al., 2012, Yang et al., 2014). Here, we present U-Pb ages and Sm-Nd isotope analyses of twelve natural titanite crystals (12YQ82, T004, Ontario, BLR-1, OLT1, Khan, Qinghu, TLS-36, NW-IOA, C253, Pakistan and MKED1) acquired by Agilent 7500a Q-ICP-MS and Neptune MC-ICP-MS, respectively, combined a 193 nm ArF excimer laser ablation system. For U-Pb dating, elemental fractionation and instrumental drift were externally corrected using MKED1 titanite standard, showing results of U-Pb analyses all within error of those recommended values. With respect to Sm-Nd isotopes, we employed the interference-free 147Sm/149Sm to deduct 144Sm isobaric interference on 144Nd, and the fractionation between 147Sm and 144Nd was calibrated using BLR-1 titanite, which is proved homogenous in Sm-Nd isotopic system. The obtained Sm-Nd isotopic compositions for natural titanite samples are all consistent with those values determined by isotope dilution (ID) MC-ICP-MS, demonstrating the precision and accuracy currently available for in situ Sm-Nd analyses. Our results demonstrate that BLR-1, OLT1 and Ontario titanites are relatively uniform and homogeneous in Sm-Nd isotopic system and thus can serve as ideal reference materials for external calibration during in situ Sm-Nd analysis.

Multiple Method Analysis of TiO2 Nanoparticle Uptake in Rice (Oryza sativa L.) Plants.

PubMed

Deng, Yingqing; Petersen, Elijah J; Challis, Katie E; Rabb, Savelas A; Holbrook, R David; Ranville, James F; Nelson, Bryant C; Xing, Baoshan

2017-09-19

Understanding the translocation of nanoparticles (NPs) into plants is challenging because qualitative and quantitative methods are still being developed and the comparability of results among different methods is unclear. In this study, uptake of titanium dioxide NPs and larger bulk particles (BPs) in rice plant (Oryza sativa L.) tissues was evaluated using three orthogonal techniques: electron microscopy, single-particle inductively coupled plasma mass spectroscopy (spICP-MS) with two different plant digestion approaches, and total elemental analysis using ICP optical emission spectroscopy. In agreement with electron microscopy results, total elemental analysis of plants exposed to TiO 2 NPs and BPs at 5 and 50 mg/L concentrations revealed that TiO 2 NPs penetrated into the plant root and resulted in Ti accumulation in above ground tissues at a higher level compared to BPs. spICP-MS analyses revealed that the size distributions of internalized particles differed between the NPs and BPs with the NPs showing a distribution with smaller particles. Acid digestion resulted in higher particle numbers and the detection of a broader range of particle sizes than the enzymatic digestion approach, highlighting the need for development of robust plant digestion procedures for NP analysis. Overall, there was agreement among the three techniques regarding NP and BP penetration into rice plant roots and spICP-MS showed its unique contribution to provide size distribution information.

Determination of (187)Os in molybdenite by ICP-MS with neutron-induced (186)Os and (188)Os spikes.

PubMed

Qu, W; Du, A; Zhao, D

2001-10-31

The article describes a method for the determination of (187)Os in molybdenite by isotope dilution inductively coupled plasma-mass spectrometry (ID-ICP-MS) with neutron-induced (186)Os and (188)Os spike. The spike used in the present work was prepared in line with the principle by which artificial nuclides are produced in a nuclear reaction. The concentration and isotopic composition of osmium in the prepared spike were evaluated accurately with the isotope dilution method, using negative thermal ion mass spectrometry (N-TIMS). The advantage of this method is that using (186)Os and (188)Os double spikes can effectively compensate for the mass discrimination effects of ICP-MS. Thus, the common correction practice for mass bias in the isotope dilution method with a single spike is unnecessary. In addition, the method enables one to reduce the determined error arising from instrumental instability. The precision for the (187)Os/((186)Os+(188)Os) ratio was approximately 2% (2sigma, RSD), but in the case of (187)Os/(186)Os, (187)Os/(188)Os and (186)Os/(188)Os, precision ranged from 2.0 to 8% (2sigma, RSD). The results for (187)Os concentration in a molybdenite sample determined with this method showed good agreement with reference values.

Practical limitations of single particle ICP-MS in the determination of nanoparticle size distributions and dissolution: case of rare earth oxides.

PubMed

Fréchette-Viens, Laurie; Hadioui, Madjid; Wilkinson, Kevin J

2017-01-15

The applicability of single particle ICP-MS (SP-ICP-MS) for the analysis of nanoparticle size distributions and the determination of particle numbers was evaluated using the rare earth oxide, La 2 O 3 , as a model particle. The composition of the storage containers, as well as the ICP-MS sample introduction system were found to significantly impact SP-ICP-MS analysis. While La 2 O 3 nanoparticles (La 2 O 3 NP) did not appear to interact strongly with sample containers, adsorptive losses of La 3+ (over 24h) were substantial (>72%) for fluorinated ethylene propylene bottles as opposed to polypropylene (<10%). Furthermore, each part of the sample introduction system (nebulizers made of perfluoroalkoxy alkane (PFA) or glass, PFA capillary tubing, and polyvinyl chloride (PVC) peristaltic pump tubing) contributed to La 3+ adsorptive losses. On the other hand, the presence of natural organic matter in the nanoparticle suspensions led to a decreased adsorptive loss in both the sample containers and the introduction system, suggesting that SP-ICP-MS may nonetheless be appropriate for NP analysis in environmental matrices. Coupling of an ion-exchange resin to the SP-ICP-MS led to more accurate determinations of the La 2 O 3 NP size distributions. Copyright © 2016 Elsevier B.V. All rights reserved.

Evaluation of methods for trace-element determination with emphasis on their usability in the clinical routine laboratory.

PubMed

Bolann, B J; Rahil-Khazen, R; Henriksen, H; Isrenn, R; Ulvik, R J

2007-01-01

Commonly used techniques for trace-element analysis in human biological material are flame atomic absorption spectrometry (FAAS), graphite furnace atomic absorption spectrometry (GFAAS), inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). Elements that form volatile hydrides, first of all mercury, are analysed by hydride generation techniques. In the absorption techniques the samples are vaporized into free, neutral atoms and illuminated by a light source that emits the atomic spectrum of the element under analysis. The absorbance gives a quantitative measure of the concentration of the element. ICP-AES and ICP-MS are multi-element techniques. In ICP-AES the atoms of the sample are excited by, for example, argon plasma at very high temperatures. The emitted light is directed to a detector, and the optical signals are processed to values for the concentrations of the elements. In ICP-MS a mass spectrometer separates and detects ions produced by the ICP, according to their mass-to-charge ratio. Dilution of biological fluids is commonly needed to reduce the effect of the matrix. Digestion using acids and microwave energy in closed vessels at elevated pressure is often used. Matrix and spectral interferences may cause problems. Precautions should be taken against trace-element contamination during collection, storage and processing of samples. For clinical problems requiring the analysis of only one or a few elements, the use of FAAS may be sufficient, unless the higher sensitivity of GFAAS is required. For screening of multiple elements, however, the ICP techniques are preferable.

Final report on CCQM-K125: elements in infant formula

NASA Astrophysics Data System (ADS)

Merrick, J.; Saxby, D.; Dutra, E. S.; Sena, R. C.; Araújo, T. O.; Almeida, M. D.; Yang, L.; Pihillagawa, I. G.; Mester, Z.; Sandoval, S.; Wei, C.; Castillo, M. E. D.; Oster, C.; Fisicaro, P.; Rienitz, O.; Pape, C.; Schulz, U.; Jährling, R.; Görlitz, V.; Lampi, E.; Kakoulides, E.; Sin, D. W. M.; Yip, Y. C.; Tsoi, Y. T.; Zhu, Y.; Okumu, T. O.; Yim, Y. H.; Heo, S. W.; Han, M.; Lim, Y.; Osuna, M. A.; Regalado, L.; Uribe, C.; Buzoianu, M. M.; Duta, S.; Konopelko, L.; Krylov, A.; Shin, R.; Linsky, M.; Botha, A.; Magnusson, B.; Haraldsson, C.; Thiengmanee, U.; Klich, H.; Can, S. Z.; Coskun, F. G.; Tunc, M.; Entwisle, J.; O'Reilly, J.; Hill, S.; Goenaga-Infante, H.; Winchester, M.; Rabb, S. A.; Pérez, R.

2017-01-01

CCQM-K125 was organized by the Inorganic Analysis Working Group (IAWG) of CCQM to assess and document the capabilities of the national metrology institutes (NMIs) or the designated institutes (DIs) to measure the mass fractions of trace elements (K, Cu and I) in infant formula. Government Laboratory, Hong Kong SAR (GLHK) acted as the coordinating laboratory. In CCQM-K125, 25 institutes submitted the results for potassium, 24 institutes submitted the results for copper and 8 institutes submitted the results for iodine. For examination of potassium and copper, most of the participants used microwave-assisted acid digestion methods for sample dissolution. A variety of instrumental techniques including inductively coupled plasma mass spectrometry (ICP-MS), isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS), inductively coupled plasma optical emission spectrometry (ICP-OES), atomic absorption spectrometry (AAS), flame atomic emission spectrometry (FAES) and microwave plasma atomic emission spectroscopy (MP-AES) were employed by the participants for determination. For analysis of iodine, most of the participants used alkaline extraction methods for sample preparation. ICP-MS and ID-ICP-MS were used by the participants for the determination. Generally, the participants' results of CCQM-K125 were found consistent for all measurands according to their equivalence statements. Except with some extreme values, most of the participants obtained the values of di/U(di) within +/- 1 for the measurands. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Method optimization and quality assurance in speciation analysis using high performance liquid chromatography with detection by inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Larsen, Erik H.

1998-02-01

Achievement of optimum selectivity, sensitivity and robustness in speciation analysis using high performance liquid chromatography (HPLC) with inductively coupled mass spectrometry (ICP-MS) detection requires that each instrumental component is selected and optimized with a view to the ideal operating characteristics of the entire hyphenated system. An isocratic HPLC system, which employs an aqueous mobile phase with organic buffer constituents, is well suited for introduction into the ICP-MS because of the stability of the detector response and high degree of analyte sensitivity attained. Anion and cation exchange HPLC systems, which meet these requirements, were used for the seperation of selenium and arsenic species in crude extracts of biological samples. Furthermore, the signal-to-noise ratios obtained for these incompletely ionized elements in the argon ICP were further enhanced by a factor of four by continously introducing carbon as methanol via the mobile phase into the ICP. Sources of error in the HPLC system (column overload), in the sample introduction system (memory by organic solvents) and in the ICP-MS (spectroscopic interferences) and their prevention are also discussed. The optimized anion and cation exchange HPLC-ICP-MS systems were used for arsenic speciation in contaminated ground water and in an in-house shrimp reference sample. For the purpose of verification, HPLC coupled with tandem mass spectrometry with electrospray ionization was additionally used for arsenic speciation in the shrimp sample. With this analytical technique the HPLC retention time in combination with mass analysis of the molecular ions and their collision-induced fragments provide almost conclusive evidence of the identity of the analyte species. The speciation methods are validated by establishing a mass balance of the analytes in each fraction of the extraction procedure, by recovery of spikes and by employing and comparing independent techniques. The urgent need for reference materials certified for elemental species is stressed.

SR-XFA as a method of choice in the search of signals of changing palaeoclimates in the sediments of Lake Baikal, compared to INAA and ICP-MS

NASA Astrophysics Data System (ADS)

Phedorin, M. A.; Bobrov, V. A.; Goldberg, E. L.; Navez, J.; Zolotaryov, K. V.; Grachev, M. A.

2000-06-01

Sediments of Lake Baikal obtained on top of the underwater Akademichesky Ridge for reconstruction of the palaeoclimates of Holocene and Upper Pleistocene were subjected to elemental analysis with three methods: (i) synchrotron radiation X-ray fluorescent analysis (SR-XFA); (ii) instrumental neutron activation analysis (INAA); (iii) induction-coupled plasma mass-spectrometry (ICP-MS). Comparison of the results obtained is accompanied by statistical tests and shows that, due to its high sensitivity, simplicity, and non-destructive nature, SR-XFA can be recommended as a method of choice in the search of geochemical signals of changing palaeoclimates.

Development of analytical methods for multiplex bio-assay with inductively coupled plasma mass spectrometry.

PubMed

Ornatsky, Olga I; Kinach, Robert; Bandura, Dmitry R; Lou, Xudong; Tanner, Scott D; Baranov, Vladimir I; Nitz, Mark; Winnik, Mitchell A

2008-01-01

Advances in the development of highly multiplexed bio-analytical assays with inductively coupled plasma mass spectrometry (ICP-MS) detection are discussed. Use of novel reagents specifically designed for immunological methods utilizing elemental analysis is presented. The major steps of method development, including selection of elements for tags, validation of tagged reagents, and examples of multiplexed assays, are considered in detail. The paper further describes experimental protocols for elemental tagging of antibodies, immunostaining of live and fixed human leukemia cells, and preparation of samples for ICP-MS analysis. Quantitative analysis of surface antigens on model cell lines using a cocktail of seven lanthanide labeled antibodies demonstrated high specificity and concordance with conventional immunophenotyping.

Determination of glyphosate and phosphate in water by ion chromatography--inductively coupled plasma mass spectrometry detection.

PubMed

Guo, Zhong-Xian; Cai, Qiantao; Yang, Zhaoguang

2005-12-30

Quantitative determination of trace glyphosate and phosphate in waters was achieved by coupling ion chromatography (IC) separation with inductively coupled plasma mass spectrometry (ICP-MS) detection. The separation of glyphosate and phosphate on a polymer anion-exchange column (Dionex IonPac AS16, 4.0 mm x 250 mm) was obtained by eluting them with 20 mM citric acid at 0.50 mL min(-1), and the analytes were detected directly and selectively by ICP-MS at m/z = 31. Parameters affecting their chromatographic behaviors and ICP-MS characteristics were systematically examined. Based on a 500-microL sample injection volume, the detection limits were 0.7 microgL(-1) for both glyphosate and phosphate, and the calibrations were linear up to 400 microgL(-1). Polyphosphates, aminomethylphosphonic acid (the major metabolite of glyphosate), non-polar and other polar phosphorus-containing pesticides showed different chromatographic behaviors from the analytes of interest and therefore did not interference. The determination was also interference free from the matrix anions (nitrate, nitrite, sulphate, chloride, etc.) and metallic ions. The analysis of certified reference material, drinking water, reservoir water and Newater yielded satisfactory results with spiked recoveries of 97.1-107.0% and relative standard deviations of < or = 7.4% (n = 3). Compared to other reported methods for glyphosate and phosphate, the developed IC-ICP-MS method is sensitive and simple, and does not require any chemical derivatization, sample preconcentration and mobile phase conductivity suppression.

A comparison of reliability of soil Cd determination by standard spectrometric methods

PubMed Central

McBride, M.B.

2015-01-01

Inductively coupled plasma emission spectrometry (ICP-OES) is the most common method for determination of soil Cd, yet spectral and matrix interferences affect measurements at the available analytical wavelengths for this metal. This study evaluated the severity of the interference over a range of total soil Cd by comparing ICP-OES and ICP-MS measurements of Cd in acid digests. ICP-OES using the emission at 226.5 nm generally unable to quantify soil Cd at low (near-background) levels, and gave unreliable values compared to ICP-MS. Using the line at 228.nm, a marked positive bias in Cd measurement (relative to the 226.5 nm measurement) was attributable to As interference even at soil As concentrations below 10 mg/kg. This spectral interference in ICP-OES was severe in As-contaminated orchard soils, giving a false value for soil total Cd near 2 mg kg−1 when soil As was 100–150 mg kg−1. In attempting to avoid these ICP emission-specific interferences, we evaluated a method to estimate total soil Cd using 1 M HNO3 extraction followed by determination of Cd by flame atomic absorption (FAA), either with or without pre-concentration of Cd using an Aliquat-heptanone extractant. The 1 M HNO3 extracted an average of 82% of total soil Cd. The FAA method had no significant interferences, and estimated the total Cd concentrations in all soils tested with acceptable accuracy. For Cd-contaminated soils, the Aliquat-heptanone pre-concentration step was not necessary, as FAA sensitivity was adequate for quantification of extractable soil Cd and reliable estimation of total soil Cd. PMID:22031569

Label-free DNA hybridization detection and single base-mismatch discrimination using CE-ICP-MS assay.

PubMed

Li, Yan; Sun, Shao-kai; Yang, Jia-lin; Jiang, Yan

2011-12-07

Detecting a specific DNA sequence and discriminating single base-mismatch is critical to clinical diagnosis, paternity testing, forensic sciences, food and drug industry, pathology, genetics, environmental monitoring, and anti-bioterrorism. To this end, capillary electrophoresis (CE) coupled with the inductively coupled plasma mass spectrometry (ICP-MS) method is developed using the displacing interaction between the target ssDNA and the competitor Hg(2+) for the first time. The thymine-rich capture ssDNA 1 is interacted with the competitor Hg(2+), forming an assembled complex in a hairpin-structure between the thymine bases arrangement at both sides of the capture ssDNA 1. In the presence of a target ssDNA with stronger affinity than that of the competitor Hg(2+), the energetically favorable hybridization between capture ssDNA 1 and the target ssDNA destroys the hairpin-structure and releases the competitor as free Hg(2+), which was then read out and accurately quantified by CE-ICP-MS assay. Under the optimal CE separation conditions, free Hg(2+) ions and its capture ssDNA 1 adduct were baseline separated and detected on-line by ICP-MS; the increased peak intensity of free Hg(2+) against the concentration of perfectly complementary target ssDNA was linear over the concentration range of 30-600 nmol L(-1) with a limit of detection of 8 nmol L(-1) (3s, n = 11) in the pre-incubated mixture containing 1 μmol L(-1) Hg(2+) and 0.2 μmol L(-1) capture ssDNA 1. This new assay method is simple in design since any target ssDNA binding can in principle result in free Hg(2+) release by 6-fold Hg(2+) signal amplification, avoiding oligonucleotide labeling or assistance by excess signal transducer and signal reporter to read out the target. Due to element-specific detection of ICP-MS in our assay procedure, the interference from the autofluorescence of substrata was eliminated.

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

USGS Publications Warehouse

May, T.W.; Wiedmeyer, Ray H.; Brumbaugh, W.G.; Schmitt, C.J.

1997-01-01

Concentrations of metals in sediment interstitial water (pore water) and those extractable from sediment with weak acids can provide important information about the bioavailability and toxicological effects of such contaminants. The highly variable nature of metal concentrations in these matrices requires instrumentation with the detection limit capability of graphite furnace atomic absorption and the wide dynamic linear range capability of ICP-OES. These criteria are satisfied with ICP-MS instrumentation. We investigated the performance of ICP-MS in the determination of certain metals from these matrices. The results for three metals were compared to those determined by graphite furnace atomic absorption spectroscopy. It was concluded that ICP-MS was an excellent instrumental approach for the determination of metals in these matrices.

A critical review of inductively coupled plasma-mass spectrometry for geoanalysis, geochemistry and hydrology, Part 1. Analytical performance

USGS Publications Warehouse

Brenner, I.B.; Taylor, Howard E.

1992-01-01

Present-day inductively coupled plasma-mass spectrometry (ICP-MS) instrumentation is described briefly. Emphasis is placed on performance characteristics for geoanalysis, geochemistry, and hydrology. Applications where ICP-MS would be indispensable are indicated. Determination of geochemically diagnostic trace elements (such as the rare earth elements [REE], U and Th), of isotope ratios for fingerprinting, tracer and other geo-isotope applications, and benchmark isotope dilution determinations are considered to be typical priority applications for ICP-MS. It is concluded that ICP-MS furnishes unique geoanalytical and environmental data that are not readily provided by conventional spectroscopic (emission and absorption) techniques.

Provenance establishment of coffee using solution ICP-MS and ICP-AES.

PubMed

Valentin, Jenna L; Watling, R John

2013-11-01

Statistical interpretation of the concentrations of 59 elements, determined using solution based inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma emission spectroscopy (ICP-AES), was used to establish the provenance of coffee samples from 15 countries across five continents. Data confirmed that the harvest year, degree of ripeness and whether the coffees were green or roasted had little effect on the elemental composition of the coffees. The application of linear discriminant analysis and principal component analysis of the elemental concentrations permitted up to 96.9% correct classification of the coffee samples according to their continent of origin. When samples from each continent were considered separately, up to 100% correct classification of coffee samples into their countries, and plantations of origin was achieved. This research demonstrates the potential of using elemental composition, in combination with statistical classification methods, for accurate provenance establishment of coffee. Copyright © 2013 Elsevier Ltd. All rights reserved.

Quantification of methionine and selenomethionine in biological samples using multiple reaction monitoring high performance liquid chromatography tandem mass spectrometry (MRM-HPLC-MS/MS).

PubMed

Vu, Dai Long; Ranglová, Karolína; Hájek, Jan; Hrouzek, Pavel

2018-05-01

Quantification of selenated amino-acids currently relies on methods employing inductively coupled plasma mass spectrometry (ICP-MS). Although very accurate, these methods do not allow the simultaneous determination of standard amino-acids, hampering the comparison of the content of selenated versus non-selenated species such as methionine (Met) and selenomethionine (SeMet). This paper reports two approaches for the simultaneous quantification of Met and SeMet. In the first approach, standard enzymatic hydrolysis employing Protease XIV was applied for the preparation of samples. The second approach utilized methanesulfonic acid (MA) for the hydrolysis of samples, either in a reflux system or in a microwave oven, followed by derivatization with diethyl ethoxymethylenemalonate. The prepared samples were then analyzed by multiple reaction monitoring high performance liquid chromatography tandem mass spectrometry (MRM-HPLC-MS/MS). Both approaches provided platforms for the accurate determination of selenium/sulfur substitution rate in Met. Moreover the second approach also provided accurate simultaneous quantification of Met and SeMet with a low limit of detection, low limit of quantification and wide linearity range, comparable to the commonly used gas chromatography mass spectrometry (GC-MS) method or ICP-MS. The novel method was validated using certified reference material in conjunction with the GC-MS reference method. Copyright © 2018. Published by Elsevier B.V.

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

PubMed

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

2015-12-01

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

Determination of mercury compounds in fish by microwave-assisted extraction and liquid chromatography-vapor generation-inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Chiou, Chwei-Sheng; Jiang, Shiuh-Jen; Kumar Danadurai, K. Suresh

2001-07-01

A method employing a vapor generation system and LC combined with inductively coupled plasma mass spectrometry (LC-ICP-MS) is presented for the determination of mercury in biological tissues. An open vessel microwave digestion system was used to extract the mercury compounds from the sample matrix. The efficiency of the mobile phase, a mixture of L-cysteine and 2-mercaptoethanol, was evaluated for LC separation of inorganic mercury [Hg(II)], methylmercury (methyl-Hg) and ethylmercury (ethyl-Hg). The sensitivity, detection limits and repeatability of the liquid chromatography (LC) ICP-MS system with a vapor generator were comparable to, or better than, that of an LC-ICP-MS system with conventional pneumatic nebulization, or other sample introduction techniques. The experimental detection limits for various mercury species were in the range of 0.05-0.09 ng ml -1 Hg, based on peak height. The proposed method was successfully applied to the determination of mercury compounds in a swordfish sample purchased from the local market. The accuracy of the method was evaluated by analyzing a marine biological certified reference material (DORM-2, NRCC).

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

USGS Publications Warehouse

May, T.W.; Wiedmeyer, Ray H.; Brown, L.D.; Casteel, S.W.

1999-01-01

In the United States lead is an ubiquitous environmental pollutant that is a serious human health hazard, especially for women of childbearing age, developing fetuses, and young children. Information concerning the uptake and distribution of lead to maternal and fetal tissues during pregnancy is poorly documented. A study was designed using domestic swine and lead isotope enrichment methodology to focus on maternal absorption and distribution of lead into bone and soft tissues, including the fetal compartment, under varying conditions of oral lead exposure and during altered physiological states (pregnant vs unbred). Total lead levels and Pb207/Pb206 ratios in bone (femur and vertebra), blood, and soft tissues (liver, kidney, brain) were determined by ICP-MS. Lead in fetal tissues derived from maternal bone could be differentiated from that derived from exogenous dosing. Unbred swine absorbed much less lead than pregnant females receiving the same dose. The accuracy and precision of ICP-MS at the instrumental level and for the entire method (sample collection, digestion, and analysis) were evaluated for both Pb207/Pb206 ratios and total lead. Several changes were suggested in method design to improve both instrumental and total method precision.

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

PubMed

Loeschner, Katrin; Navratilova, Jana; Grombe, Ringo; Linsinger, Thomas P J; Købler, Carsten; Mølhave, Kristian; Larsen, Erik H

2015-08-15

Nanomaterials are increasingly used in food production and packaging, and validated methods for detection of nanoparticles (NPs) in foodstuffs need to be developed both for regulatory purposes and product development. Asymmetric flow field-flow fractionation with inductively coupled plasma mass spectrometric detection (AF(4)-ICP-MS) was applied for quantitative analysis of silver nanoparticles (AgNPs) in a chicken meat matrix following enzymatic sample preparation. For the first time an analytical validation of nanoparticle detection in a food matrix by AF(4)-ICP-MS has been carried out and the results showed repeatable and intermediately reproducible determination of AgNP mass fraction and size. The findings demonstrated the potential of AF(4)-ICP-MS for quantitative analysis of NPs in complex food matrices for use in food monitoring and control. The accurate determination of AgNP size distribution remained challenging due to the lack of certified size standards. Copyright © 2015 Elsevier Ltd. All rights reserved.

Assessing rare earth elements in quartz rich geological samples.

PubMed

Santoro, A; Thoss, V; Ribeiro Guevara, S; Urgast, D; Raab, A; Mastrolitti, S; Feldmann, J

2016-01-01

Sodium peroxide (Na2O2) fusion coupled to Inductively Coupled Plasma Tandem Mass Spectrometry (ICP-MS/MS) measurements was used to rapidly screen quartz-rich geological samples for rare earth element (REE) content. The method accuracy was checked with a geological reference material and Instrumental Neutron Activation Analysis (INAA) measurements. The used mass-mode combinations presented accurate results (only exception being (157)Gd in He gas mode) with recovery of the geological reference material QLO-1 between 80% and 98% (lower values for Lu, Nd and Sm) and in general comparable to INAA measurements. Low limits of detection for all elements were achieved, generally below 10 pg g(-1), as well as measurement repeatability below 15%. Overall, the Na2O2/ICP-MS/MS method proved to be a suitable lab-based method to quickly and accurately screen rock samples originating from quartz-rich geological areas for rare earth element content; particularly useful if checking commercial viability. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

NASA Technical Reports Server (NTRS)

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

2012-01-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 elementalmore » 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.« less

Metal-doped inorganic nanoparticles for multiplex detection of biomarkers by a sandwich-type ICP-MS immunoassay.

PubMed

Ko, Jung Aa; Lim, H B

2016-09-28

Metal-doped inorganic nanoparticles were synthesized for the multiplex detection of biomarkers by a sandwich-type inductively coupled plasma mass spectrometry (ICP-MS) immunoassay. The synthesized Cs-doped multicore magnetic nanoparticles (MMNPs) were used not only for magnetic extraction of targets but also for ratiometric measurement in ICP-MS. In addition, three different metal/dye-doped silica nanoparticles (SNPs) were synthesized as probes for multiplex detection: Y/RhBITC (rhodamine B isothiocyanate)-doped SNPs for CRP (cardiovascular disease), Cd/RhBITC-doped SNPs for AFP (tumor), and Au/5(6)-XRITC (X-rhodamine-5-(and-6)-isothiocyanate)-doped SNPs for NSE (heart disease). For quantification, the doped metals of SNPs were measured by ICP-MS and then the signal ratio to Cs of MMNPs was plotted with respect to the concentration of targets by a ratiometry. Limits of detection (LOD) of 0.35 ng/mL to 77 ng mL(-1) and recoveries of 83%-125% were obtained for serum samples spiked with the biomarkers. Since no sample treatment was necessary prior to the extraction, the proposed method provided short analysis time and convenience for the multiplex determination of biomarkers, which will be valuable for clinical application. Copyright © 2016 Elsevier B.V. All rights reserved.

Absolute measurements and certified reference material for iron isotopes using multiple-collector inductively coupled mass spectrometry.

PubMed

Zhou, Tao; Zhao, Motian; Wang, Jun; Lu, Hai

2008-01-01

Two enriched isotopes, 99.94 at.% 56Fe and 99.90 at.% 54Fe, were blended under gravimetric control to prepare ten synthetic isotope samples whose 56Fe isotope abundances ranged from 95% to 20%. For multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) measurements typical polyatomic interferences were removed by using Ar and H2 as collision gas and operating the MC-ICP-MS system in soft mode. Thus high-precision measurements of the Fe isotope abundance ratios were accomplished. Based on the measurement of the synthetic isotope abundance ratios by MC-ICP-MS, the correction factor for mass discrimination was calculated and the results were in agreement with results from IRMM014. The precision of all ten correction factors was 0.044%, indicating a good linearity of the MC-ICP-MS method for different isotope abundance ratio values. An isotopic reference material was certified under the same conditions as the instrument was calibrated. The uncertainties of ten correction factors K were calculated and the final extended uncertainties of the isotopic certified Fe reference material were 5.8363(37) at.% 54Fe, 91.7621(51) at.% 56Fe, 2.1219(23) at.% 57Fe, and 0.2797(32) at.% 58Fe.

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

USGS Publications Warehouse

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

2007-01-01

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

Green and efficient sample preparation method for the determination of catalyst residues in margarine by ICP-MS.

PubMed

Hartwig, Carla Andrade; Pereira, Rodrigo Mendes; Novo, Diogo La Rosa; Oliveira, Dirce Taina Teixeira; Mesko, Marcia Foster

2017-11-01

Responding to the need for green and efficient methods to determine catalyst residues with suitable precision and accuracy in samples with high fat content, the present work evaluates a microwave-assisted ultraviolet digestion (MW-UV) system for margarines and subsequent determination of Ni, Pd and Pt using inductively coupled plasma mass spectrometry (ICP-MS). It was possible to digest up to 500mg of margarine using only 10mL of 4molL -1 HNO 3 with a digestion efficiency higher than 98%. This allowed the determination of catalyst residues using the ICP-MS and free of interferences. For this purpose, the following experimental parameters were evaluated: concentration of digestion solution, sample mass and microwave irradiation program. The residual carbon content was used as a parameter to evaluate the efficiency of digestion and to select the most suitable experimental conditions. The accuracy evaluation was performed by recovery tests using a standard solution and certified reference material, and recoveries ranging from 94% to 99% were obtained for all analytes. The limits of detection for Ni, Pd and Pt using the proposed method were 35.6, 0.264 and 0.302ngg -1 , respectively. When compared to microwave-assisted digestion (MW-AD) in closed vessels using concentrated HNO 3 (used as a reference method for sample digestion), the proposed MW-UV could be considered an excellent alternative for the digestion of margarine, as this method requires only a diluted nitric acid solution for efficient digestion. In addition, MW-UV provides appropriate solutions for further ICP-MS determination with suitable precision (relative standard deviation < 7%) and accuracy for all evaluated analytes. The proposed method was applied to margarines from different brands produced in Brazil, and the concentration of catalyst residues was in agreement with the current legislation or recommendations. Copyright © 2017 Elsevier B.V. All rights reserved.

[Study on microwave digestion of gypsum for the determination of multielement by ICP-OES and ICP-MS].

PubMed

Wang, Hui; Song, Qiang; Yang, Rui-ming; Yao, Qiang; Chen, Chang-he

2010-09-01

Three acids (HNO3, HNO3/HF and HNO3 /HF+ H3BO3) were used to decompose gypsum with microwave digestion system. The contents of 10 mineral elements (Al, Ca, Mg, Fe, K, Na, S, Ti, Si and Sr) in gypsum were determined by inductively coupled plasma-optical emission spectrometry (ICP-OES) while 6 heavy metals (V, Cr, Mn, Zn, Se and Ce) were determined by inductively coupled plasma-mass spectrometry (ICP-MS). GBW03109a, GBW03110 and FGD-2 were used as gypsum standard reference materials. The results showed that two-step microwave digestion with HNO3/HF at 210 degrees C and then adding H3BO3 for the removal of HF and fluorides completely decomposed the gypsums, while this method achieved good recoveries for all elements in the three gypsum standard reference materials. The recovery was from 88% to 112% and the RSD of tests was below 3%. The method was applied to the elemental analysis for flue gas desulfurization gypsums from three coal-fired power plants.

A new basaltic glass microanalytical reference material for multiple techniques

USGS Publications Warehouse

Wilson, Steve; Koenig, Alan; Lowers, Heather

2012-01-01

The U.S. Geological Survey (USGS) has been producing reference materials since the 1950s. Over 50 materials have been developed to cover bulk rock, sediment, and soils for the geological community. These materials are used globally in geochemistry, environmental, and analytical laboratories that perform bulk chemistry and/or microanalysis for instrument calibration and quality assurance testing. To answer the growing demand for higher spatial resolution and sensitivity, there is a need to create a new generation of microanalytical reference materials suitable for a variety of techniques, such as scanning electron microscopy/X-ray spectrometry (SEM/EDS), electron probe microanalysis (EPMA), laser ablation inductively coupled mass spectrometry (LA-ICP-MS), and secondary ion mass spectrometry (SIMS). As such, the microanalytical reference material (MRM) needs to be stable under the beam, be homogeneous at scales of better than 10–25 micrometers for the major to ultra-trace element level, and contain all of the analytes (elements or isotopes) of interest. Previous development of basaltic glasses intended for LA-ICP-MS has resulted in a synthetic basaltic matrix series of glasses (USGS GS-series) and a natural basalt series of glasses (BCR-1G, BHVO-2G, and NKT-1G). These materials have been useful for the LA-ICP-MS community but were not originally intended for use by the electron or ion beam community. A material developed from start to finish with intended use in multiple microanalytical instruments would be useful for inter-laboratory and inter-instrument platform comparisons. This article summarizes the experiments undertaken to produce a basalt glass reference material suitable for distribution as a multiple-technique round robin material. The goal of the analytical work presented here is to demonstrate that the elemental homogeneity of the new glass is acceptable for its use as a reference material. Because the round robin exercise is still underway, only nominal compositional ranges for each element are given in the article.

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

NASA Astrophysics Data System (ADS)

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

2010-05-01

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

Advantages of reaction cell ICP-MS on doubly charged interferences for arsenic and selenium analysis in foods

PubMed Central

Jackson, Brian; Liba, Amir; Nelson, Jenny

2014-01-01

Recent reports of As concentrations in certain food and drinks have garnered public concern and led to a lowering of the US guideline maximum concentration for inorganic As in apple juice and proposed limits for As in rice products. In contrast Se is an essential micro-nutrient that can be limiting when Se-poor soils yield Se-poor food crops. Rare earth element (REE) doubly charged interferences on As and Se can be significant even when initial ICP-MS tuning minimizes doubly charged formation. We analyzed NIST 1547 (peach leaves) and 1515 (apple leaves), which contain high levels of REEs, by quadrupole ICP-MS with (He) collision mode, H2 reaction mode or triple quadrupole ICP-MS (ICP-QQQ) in mass-shift mode (O2 and O2/H2). Analysis by collision cell ICP-MS significantly over-estimated As and Se concentration due to REE doubly charged formation; mathematical correction increased the accuracy of analysis but is prone to error when analyte concentration and sensitivity is low and interferent is high. For Se, H2 reaction mode was effective in suppressing Gd2+ leading to accurate determination of Se in both SRMs without the need for mathematical correction. ICP-QQQ using mass-shift mode for As+ from m/z 75 to AsO+ at m/z 91 and Se+ from m/z 78 to SeO+ at m/z 94 alleviated doubly charged effects and resulted in accurate determination of As and Se in both SRMs without the need for correction equations. Zr and Mo isobars at 91 and 94 were shown to be effectively rejected by the MS/MS capability of the ICP-QQQ. PMID:25609851

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

NASA Astrophysics Data System (ADS)

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

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

A Comprehensive Evaluation of Steroid Metabolism in Women with Intrahepatic Cholestasis of Pregnancy

PubMed Central

Pařízek, Antonín; Hill, Martin; Dušková, Michaela; Vítek, Libor; Velíková, Marta; Kancheva, Radmila; Šimják, Patrik; Koucký, Michal; Kokrdová, Zuzana; Adamcová, Karolína; Černý, Andrej; Hájek, Zdeněk; Stárka, Luboslav

2016-01-01

Intrahepatic cholestasis of pregnancy (ICP) is a common liver disorder, mostly occurring in the third trimester. ICP is defined as an elevation of serum bile acids, typically accompanied by pruritus and elevated activities of liver aminotransferases. ICP is caused by impaired biliary lipid secretion, in which endogenous steroids may play a key role. Although ICP is benign for the pregnant woman, it may be harmful for the fetus. We evaluated the differences between maternal circulating steroids measured by RIA (17-hydroxypregnenolone and its sulfate, 17-hydroxyprogesterone, and cortisol) and GC-MS (additional steroids), hepatic aminotransferases and bilirubin in women with ICP (n = 15, total bile acids (TBA) >8 μM) and corresponding controls (n = 17). An age-adjusted linear model, receiver-operating characteristics (ROC), and multivariate regression (a method of orthogonal projections to latent structure, OPLS) were used for data evaluation. While aminotransferases, conjugates of pregnanediols, 17-hydroxypregnenolone and 5β-androstane-3α,17β-diol were higher in ICP patients, 20α-dihydropregnenolone, 16α-hydroxy-steroids, sulfated 17-oxo-C19-steroids, and 5β-reduced steroids were lower. The OPLS model including steroids measured by GC-MS and RIA showed 93.3% sensitivity and 100% specificity, while the model including steroids measured by GC-MS in a single sample aliquot showed 93.3% sensitivity and 94.1% specificity. A composite index including ratios of sulfated 3α/β-hydroxy-5α/β-androstane-17-ones to conjugated 5α/β-pregnane-3α/β, 20α-diols discriminated with 93.3% specificity and 81.3% sensitivity (ROC analysis). These new data demonstrating altered steroidogenesis in ICP patients offer more detailed pathophysiological insights into the role of steroids in the development of ICP. PMID:27494119

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.

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

USGS Publications Warehouse

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

2004-01-01

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

Interference-free determination of sub ng kg-1 levels of long-lived 93Zr in the presence of high concentrations (μg kg-1) of 93Mo and 93Nb using ICP-MS/MS.

PubMed

Petrov, Panayot; Russell, Ben; Douglas, David N; Goenaga-Infante, Heidi

2018-01-01

Long-lived high abundance radionuclides are of increasing interest with regard to decommissioning of nuclear sites and longer term nuclear waste storage and disposal. In many cases, no routine technique is available for their measurement in nuclear waste and low-level (ng kg -1 ) environmental samples. Recent advances in ICP-MS technology offer attractive features for the selective and sensitive determination of a wide range of long-lived radionuclides. In this work, inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS)-based methodology, suitable for accurate routine determinations of 93 Zr at very low (ng kg -1 ) levels in the presence of high levels (μg kg -1 ) of the isobaric interferents 93 Nb and 93 Mo (often present in nuclear waste samples), is reported for the first time. Additionally, a novel and systematic strategy for method development based on the use of non-radioactive isotopes is proposed. It relies on gas-phase chemical reactions for different molecular ion formation to achieve isobaric interference removal. Using cell gas mixtures of NH 3 /He/H 2 or H 2 /O 2 , and suitable mass shifts, the signal from the 93 Nb and 93 Mo isobaric interferences on 93 Zr were suppressed by up to 5 orders of magnitude. The achieved limit of detection for 93 Zr was 1.3 × 10 -5  Bq g -1 (equivalent to 0.14 ng kg -1 ). The sample analysis time is 2 min, which represents a significant improvement in terms of sample throughput, compared to liquid scintillation counting methods. The method described here can be used for routine measurements of 93 Zr at environmentally relevant levels. It can also be combined with radiometric techniques for use towards the standardisation of 93 Zr measurements. Graphical abstract Interference-free determination of 93 Zr in the presence of high concentrations of isobaric 93 Mo and 93 Nb by ICP-MS/MS.

A simple micro-photometric method for urinary iodine determination.

PubMed

Grimm, Gabriele; Lindorfer, Heidelinde; Kieweg, Heidi; Marculescu, Rodrig; Hoffmann, Martha; Gessl, Alois; Sager, Manfred; Bieglmayer, Christian

2011-10-01

Urinary iodide concentration (UIC) is useful to evaluate nutritional iodine status. In clinical settings UIC helps to exclude blocking of the thyroid gland by excessive endogenous iodine, if diagnostic or therapeutic administration of radio-iodine is indicated. Therefore, this study established a simple test for the measurement of UIC. UIC was analyzed in urine samples of 200 patients. Samples were pre-treated at 95°C for 45 min with ammonium persulfate in a thermal cycler, followed by a photometric Sandell-Kolthoff reaction (SK) carried out in microtiter plates. For method comparison, UIC was analyzed in 30 samples by inductivity coupled plasma mass spectro-metry (ICP-MS) as a reference method. Incubation conditions were optimized concerning recovery. The photometric test correlated well to the reference method (SK=0.91*ICP-MS+1, r=0.962) and presented with a functional sensitivity of 20 μg/L. UIC of patient samples ranged from <20 to 750 μg/L (median 110 μg/L); 90% of the urine samples had iodide concentrations below 210 μg/L. The modified SK-test takes approximately 90 min for analyses of 20 urine samples compared with 27 h for ICP-MS. The photometric test provides satisfactory results and can be performed with the basic equipment of a clinical laboratory.

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

PubMed

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

2014-02-01

A novel Fe3O4@SiO2@polyaniline-graphene oxide composite (MPANI-GO) was prepared through a simple noncovalent method and applied to magnetic solid phase extraction (MSPE) of trace rare earth elements (REEs) in tea leaves and environmental water samples followed by inductively coupled plasma mass spectrometry (ICP-MS) detection. The prepared MPANI-GO was characterized by transmission electron microscopy and vibrating sample magnetometer. Various parameters affecting MPANI-GO MSPE of REEs have been investigated. Under the optimized conditions, the limits of detection (LODs, 3σ) for REEs were in the range of 0.04-1.49 ng L(-1) and the relative standard deviations (RSDs, c=20 ng L(-1), n=7) were 1.7-6.5%. The accuracy of the proposed method was validated by analyzing a Certified Reference Material of GBW 07605 tea leaves. The method was also successfully applied for the determination of trace REEs in tea leaves and environmental water samples. The developed MPANI-GO MSPE-ICP-MS method has the advantages of simplicity, rapidity, high sensitivity, high enrichment factor and is suitable for the analysis of trace REEs in samples with complex matrix. © 2013 Elsevier B.V. All rights reserved.

Prospects for dating monazite via single-collector HR-ICP-MS

NASA Astrophysics Data System (ADS)

Kohn, M. J.; Vervoort, J. D.

2006-12-01

ICP-MS analysis permits rapid and precise dating of minerals with high U and Th contents. Here we describe a new method for in situ determination of 206Pb/238U, 207Pb/^{235}U, ^{208}Pb/232Th, and 207Pb/206Pb ages in monazite via laser ablation (New Wave Research UP-213 laser system), single-collector, magnetic sector ICP-MS (ThermoFinnigan Element2), using spot sizes of 8-30 μm, a repetition rate of 5 Hz, and a fluence of 10 J/cm2. Based on analysis of 9 monazite samples of known ages ranging from 280 to 1800 Ma, analytical precision (single sample) is ±2-3% (2σ), and reproducibility (single sample) is ±2-4% (2σ), yielding age precisions of ±3- 5% (2σ) for single points, or ±1-2% (2 s.e.) for pooled multiple analyses (n > 4). Issues of accuracy are paramount. 207Pb/206Pb ages are consistently the most accurate and agree to ±2% with accepted TIMS ages. In contrast, 206Pb/238U, 207Pb/^{235}U, and ^{208}Pb/232Th ages can differ by as much as ±5% (2σ), a problem that has also been observed for SIMS Th-Pb dating. The sources of the interelement standardization disparities among monazites remain enigmatic, but do not result from molecular interferences on Pb, U, or Th peaks. Unresolvable mass interference between 204Pb and trace contaminant 204Hg in commercial Ar gas precludes precise common Pb corrections. Instead common Pb corrections are made assuming concordancy between 207Pb/^{235}U and either 206Pb/238U or ^{208}Pb/232Th ages. The new method offers rapid analysis (~1 minute), minimal sample preparation (polished thin section), and high sensitivity. Comparatively large errors on the 206Pb/238U, 207Pb/^{235}U, and ^{208}Pb/232Th ages will likely restrict analysis of younger monazite grains (<250 Ma) to applications where 5% accuracy is sufficient. Older grains (c. 500 Ma and older) can be dated more precisely and accurately using 207Pb/206Pb. One application to young materials involves dating a large vein monazite from the Llallagua tin district of Bolivia, which resolves a ~2 Myr history of mineralization at 20-22 Ma. These data support mineralization age estimates of 21 Ma (K-Ar on wallrock minerals) rather than 44 Ma (Sm-Nd on apatite).

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

PubMed

Marcinkowska, Monika; Barałkiewicz, Danuta

2016-12-01

Speciation analysis has become an invaluable tool in human health risk assessment, environmental monitoring or food quality control. Another step is to develop reliable multielemental speciation methodologies, to reduce costs, waste and time needed for the analysis. Separation and detection of species of several elements in a single analytical run can be accomplished by high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC/ICP-MS). Our review assembles articles concerning multielemental speciation determination of: As, Se, Cr, Sb, I, Br, Pb, Hg, V, Mo, Te, Tl, Cd and W in environmental, biological, food and clinical samples analyzed with HPLC/ICP-MS. It addresses the procedures in terms of following issues: sample collection and pretreatment, selection of optimal conditions for elements species separation by HPLC and determination using ICP-MS as well as metrological approach. The presented work is the first review article concerning multielemental speciation analysis by advanced hyphenated technique HPLC/ICP-MS. Copyright © 2016 Elsevier B.V. All rights reserved.

An in-depth evaluation of accuracy and precision in Hg isotopic analysis via pneumatic nebulization and cold vapor generation multi-collector ICP-mass spectrometry.

PubMed

Rua-Ibarz, Ana; Bolea-Fernandez, Eduardo; Vanhaecke, Frank

2016-01-01

Mercury (Hg) isotopic analysis via multi-collector inductively coupled plasma (ICP)-mass spectrometry (MC-ICP-MS) can provide relevant biogeochemical information by revealing sources, pathways, and sinks of this highly toxic metal. In this work, the capabilities and limitations of two different sample introduction systems, based on pneumatic nebulization (PN) and cold vapor generation (CVG), respectively, were evaluated in the context of Hg isotopic analysis via MC-ICP-MS. The effect of (i) instrument settings and acquisition parameters, (ii) concentration of analyte element (Hg), and internal standard (Tl)-used for mass discrimination correction purposes-and (iii) different mass bias correction approaches on the accuracy and precision of Hg isotope ratio results was evaluated. The extent and stability of mass bias were assessed in a long-term study (18 months, n = 250), demonstrating a precision ≤0.006% relative standard deviation (RSD). CVG-MC-ICP-MS showed an approximately 20-fold enhancement in Hg signal intensity compared with PN-MC-ICP-MS. For CVG-MC-ICP-MS, the mass bias induced by instrumental mass discrimination was accurately corrected for by using either external correction in a sample-standard bracketing approach (SSB) or double correction, consisting of the use of Tl as internal standard in a revised version of the Russell law (Baxter approach), followed by SSB. Concomitant matrix elements did not affect CVG-ICP-MS results. Neither with PN, nor with CVG, any evidence for mass-independent discrimination effects in the instrument was observed within the experimental precision obtained. CVG-MC-ICP-MS was finally used for Hg isotopic analysis of reference materials (RMs) of relevant environmental origin. The isotopic composition of Hg in RMs of marine biological origin testified of mass-independent fractionation that affected the odd-numbered Hg isotopes. While older RMs were used for validation purposes, novel Hg isotopic data are provided for the latest generations of some biological RMs.

EXTRACTION AND DETECTION OF A NEW ARSINE SULFIDE CONTAINING ARSENOSUGAR IN MOLLUSCS BY IC-ICP-MS AND IC-ESI-MS/MS

EPA Science Inventory

Using IC-ICP-MS and IC-ESI-MS/MS, an unknown arsenical compound in mollusks has been identified as a new arsine sulfide containing analog of a known arsenosugar and is referred to as As(498). This species has been observed in four separate shellfish species following a mild metha...

GSD-1G and MPI-DING Reference Glasses for In Situ and Bulk Isotopic Determination

USGS Publications Warehouse

Jochum, K.P.; Wilson, S.A.; Abouchami, W.; Amini, M.; Chmeleff, J.; Eisenhauer, A.; Hegner, E.; Iaccheri, L.M.; Kieffer, B.; Krause, J.; McDonough, W.F.; Mertz-Kraus, R.; Raczek, I.; Rudnick, R.L.; Scholz, Donna K.; Steinhoefel, G.; Stoll, B.; Stracke, A.; Tonarini, S.; Weis, D.; Weis, U.; Woodhead, J.D.

2011-01-01

This paper contains the results of an extensive isotopic study of United States Geological Survey GSD-1G and MPI-DING reference glasses. Thirteen different laboratories were involved using high-precision bulk (TIMS, MC-ICP-MS) and microanalytical (LA-MC-ICP-MS, LA-ICP-MS) techniques. Detailed studies were performed to demonstrate the large-scale and small-scale homogeneity of the reference glasses. Together with previously published isotopic data from ten other laboratories, preliminary reference and information values as well as their uncertainties at the 95% confidence level were determined for H, O, Li, B, Si, Ca, Sr, Nd, Hf, Pb, Th and U isotopes using the recommendations of the International Association of Geoanalysts for certification of reference materials. Our results indicate that GSD-1G and the MPI-DING glasses are suitable reference materials for microanalytical and bulk analytical purposes. Ce document contient les r??sultats d'une importante ??tude isotopique des verres de r??f??rence USGS GSD-1G et MPI-DING. Treize laboratoires diff??rents ont particip?? au travers de techniques analytiques de haute pr??cision travaillant soit sur ??chantillon total (TIMS, MC-ICP-MS) soit par microanalyse ??in situ?? (LA-MC-ICP-MS, LA-ICP-MS). ?? 2010 The Authors. Geostandards and Geoanalytical Research ?? 2010 International Association of Geoanalysts.

Development of analytical methods for multiplex bio-assay with inductively coupled plasma mass spectrometry

PubMed Central

Ornatsky, Olga I.; Kinach, Robert; Bandura, Dmitry R.; Lou, Xudong; Tanner, Scott D.; Baranov, Vladimir I.; Nitz, Mark; Winnik, Mitchell A.

2008-01-01

Advances in the development of highly multiplexed bio-analytical assays with inductively coupled plasma mass spectrometry (ICP-MS) detection are discussed. Use of novel reagents specifically designed for immunological methods utilizing elemental analysis is presented. The major steps of method development, including selection of elements for tags, validation of tagged reagents, and examples of multiplexed assays, are considered in detail. The paper further describes experimental protocols for elemental tagging of antibodies, immunostaining of live and fixed human leukemia cells, and preparation of samples for ICP-MS analysis. Quantitative analysis of surface antigens on model cell lines using a cocktail of seven lanthanide labeled antibodies demonstrated high specificity and concordance with conventional immunophenotyping. PMID:19122859

Advances in the measurement of sulfur isotopes by multi-collector ICP-MS (MC-ICP- MS)

NASA Astrophysics Data System (ADS)

Ridley, W. I.; Wilson, S. A.; Anthony, M. W.

2006-12-01

The demonstrated capability to measure 34S/32S by MC-ICP-MS with a precision (2ó) of ~0.2 per mil has many potential applications in geochemistry. However, a number of obstacles limit this potential. First, to achieve the precision indicated above requires sufficient mass resolution to separate isobaric interferences of 16O2 and 17O2 on 32S and 34S, respectively. These requirements for high resolution mean overall instrument sensitivity is reduced. Second, current methods preclude analysis of samples with complex matrices, a common characteristic of sulfur-bearing geologic materials. Here, we describe and discuss a method that provides both efficient removal of matrix constituents, and provides pre-concentration of S, thus overcoming these obstacles. The method involves the separation of sulfur from matrix constituents by high pressure (1000 psi) ion chromatography (HPIC), followed by isotope measurement using MC-ICP-MS. This combination allows for analysis of liquid samples with a wide range of S concentrations. A powerful advantage of this technique is the efficient separation of many sulfur species from matrix cations and anions (for instance in a seawater or acid mine drainage matrix), as well as the separation of sulfur species, e.g., sulfate, sulfite, thiosulfate, thiocynate, from each other for isotope analysis. The automated HPIC system uses a carbonate-bicarbonate eluent with eluent suppression, and has sufficient baseline separation to collect the various sulfur species as pure fractions. The individual fractions are collected over a specific time interval based upon a pre-determined elution profile and peak retention times. The addition of a second ion exchange column into the system allows pre-concentration of sulfur species by 2-3 orders of magnitude for samples that otherwise would have sulfur concentrations too low to provide precise isotopic ratios. The S isotope ratios are measured by MC-ICP-MS using a desolvating sample introduction system, a standard-sample bracketing method employing standards that are well characterized for sulfur isotope composition using stable isotope gas mass spectrometry. Data are collected in time-resolved mode, which reduces analytical time and allows for flexibility in data integration. Preliminary data indicates that sulfur species do not fractionate during the column chemistry.

Contribution of infrared microscopy to studies of fluid inclusions hosted in some opaque ore minerals: possibilities, limitations, and perspectives

NASA Astrophysics Data System (ADS)

Lüders, Volker

2017-06-01

During the past two decades, several studies of fluid inclusions hosted in some opaque ore minerals using near-infrared microscopy have been performed. Results indicated that this method can be applied to several sulfidic ores and metal oxides depending on their electronic band structures and infrared-active vibration modes. Infrared transmittance of individual ore minerals can be best characterized using Fourier transform infrared spectroscopy. Infrared microscopic observations are limited to the near-infrared region to about 2.3 μm depending on the IR sensitivity of the IR camera. The trace element content in ore minerals can be another limiting factor for optical observations in near-infrared light. Still, IR transmittance gradually decreases upon heating caused by shifting of IR absorption edges for higher wavelengths. Possibilities and limitations of studying fluid inclusions hosted in opaque minerals by near-infrared light microthermometry and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) are discussed.

New Ca-Tims and La-Icp Analyses of GJ-1, Plesovice, and FC1 Reference Materials

NASA Astrophysics Data System (ADS)

Feldman, J. D.; Möller, A.; Walker, J. D.

2014-12-01

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) U-Pb zircon geochronology relies on external reference standards to monitor and correct for different mass fractionation effects and instrument drift. Common zircon reference materials used within the community, including the KU Isotope Geochemistry Laboratory, are GJ-1 (207Pb/206Pb age: 608.53 +/- 0.37Ma; Jackson et al., 2004), Plesovice (337.13 +/- 0.37 Ma; Slama et al., 2008), and FC-1 (1099.0 +/-0.6 Ma; Paces and Miller, 1993). The age distribution of zircon reference material varies slightly from sample fraction to sample fraction, and the published results for GJ-1 are slightly discordant. As a result, using the published data for the distributed standard splits can lead to small systematic variations when comparing datasets from different labs, and more high precision data are needed to evaluate potential inhomogeneity of sample splits used in different laboratories. Here we characterize these reference materials with cathodoluminescence, LA-ICP-MS traverses across grains, and high precision CA-TIMS to better constrain the ages and assess zoning of these standards, and present the data for comparison with other laboratories. Reducing systematic error by dating our own reference material lends confidence to our analyses and allows for inter-laboratory age reproducibility of unknowns. Additionally, the reduction in propagated uncertainties (especially in GJ-1, for which both the red and yellow variety will be analyzed) will be used to improve long-term reproducibility, comparisons between samples of similar age, detrital populations and composite pluton zircons. Jackson, S.E., et al., 2004, Chemical Geology, v. 211, p. 47-69. Paces, J.B. & Miller, J.D., 1993, Journal of Geophysical Research, v. 80, p. 13997-14013. Slama, J., et al., 2008, Chemical Geology, v. 249. p. 1-35.

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

USGS Publications Warehouse

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

2010-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2008-11-01

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

Development and Validation of an Inductively Coupled Plasma Mass Spectrometry (ICP-MS) Method for Quantitative Analysis of Platinum in Plasma, Urine, and Tissues.

PubMed

Zhang, Ti; Cai, Shuang; Forrest, Wai Chee; Mohr, Eva; Yang, Qiuhong; Forrest, M Laird

2016-09-01

Cisplatin, a platinum chemotherapeutic, is one of the most commonly used chemotherapeutic agents for many solid tumors. In this work, we developed and validated an inductively coupled plasma mass spectrometry (ICP-MS) method for quantitative determination of platinum levels in rat urine, plasma, and tissue matrices including liver, brain, lungs, kidney, muscle, heart, spleen, bladder, and lymph nodes. The tissues were processed using a microwave accelerated reaction system (MARS) system prior to analysis on an Agilent 7500 ICP-MS. According to the Food and Drug Administration guidance for industry, bioanalytical validation parameters of the method, such as selectivity, accuracy, precision, recovery, and stability were evaluated in rat biological samples. Our data suggested that the method was selective for platinum without interferences caused by other presenting elements, and the lower limit of quantification was 0.5 ppb. The accuracy and precision of the method were within 15% variation and the recoveries of platinum for all tissue matrices examined were determined to be 85-115% of the theoretical values. The stability of the platinum-containing solutions, including calibration standards, stock solutions, and processed samples in rat biological matrices was investigated. Results indicated that the samples were stable after three cycles of freeze-thaw and for up to three months. © The Author(s) 2016.

Development and Validation of an Inductively Coupled Plasma Mass Spectrometry (ICP-MS) Method for Quantitative Analysis of Platinum in Plasma, Urine, and Tissues

PubMed Central

Zhang, Ti; Cai, Shuang; Forrest, Wai Chee; Mohr, Eva; Yang, Qiuhong; Forrest, M. Laird

2016-01-01

Cisplatin, a platinum chemotherapeutic, is one of the most commonly used chemotherapeutic agents for many solid tumors. In this work, we developed and validated an inductively coupled plasma mass spectrometry (ICP-MS) method for quantitative determination of platinum levels in rat urine, plasma, and tissue matrices including liver, brain, lungs, kidney, muscle, heart, spleen, bladder, and lymph nodes. The tissues were processed using a microwave accelerated reaction system (MARS) system prior to analysis on an Agilent 7500 ICP-MS. According to the Food and Drug Administration guidance for industry, bioanalytical validation parameters of the method, such as selectivity, accuracy, precision, recovery, and stability were evaluated in rat biological samples. Our data suggested that the method was selective for platinum without interferences caused by other presenting elements, and the lower limit of quantification was 0.5 ppb. The accuracy and precision of the method were within 15% variation and the recoveries of platinum for all tissue matrices examined were determined to be 85–115% of the theoretical values. The stability of the platinum-containing solutions, including calibration standards, stock solutions, and processed samples in rat biological matrices was investigated. Results indicated that the samples were stable after three cycles of freeze–thaw and for up to three months. PMID:27527103

On the certification of cadmium at trace and ultratrace levels in standard reference materials using ID ICP-MS.

PubMed

Murphy, K E; Long, S E; Vocke, R D

2007-04-01

Analytical methods used for the isotope dilution inductively coupled plasma mass spectrometric (ID-ICP-MS) measurement of Cd at microg kg(-1) and sub-microg kg(-1) levels are described and applied to the certification of new dietary supplement, blood, and serum Standard Reference Materials (SRMs). The materials are: SRM 3240 Ephedra sinica Stapf Aerial Parts, SRM 3241 Ephedra sinica Stapf Native Extract, SRM 3243 Ephedra-Containing Solid Oral Dosage Form, SRM 3244 Ephedra-Containing Protein Powder, SRM 966 Toxic Metals in Bovine Blood, Level 1 (L1) and Level 2 (L2), and SRM 1598a Animal Serum. The concentration of Cd in the materials ranges from 120 microg kg(-1) down to 0.03 microg kg(-1). At these levels, the factors that most influence the accuracy of the ICP-MS data are the procedure blank and spectral and nonspectral interferences. Nonspectral interference, caused by the high concentration of dissolved solids in the matrices investigated, resulted in signal suppression. Matrix separation was used to enhance signal intensity and to reduce spectral interference for the accurate determination of Cd in SRM 1598a and SRM 3244. Chromatographic separation procedures using Chelex for SRM 1598a and anion exchange for SRM 3244 were optimized to achieve the desired separation characteristics without substantially increasing the procedure blank. Sensitivity for the determination of Cd in serum was additionally enhanced through the use of desolvation nebulization. We determined that separations were not required for the accurate ICP-MS determination of Cd in SRM 3240, SRM 3241, SRM 3243, and SRM 966 L2 under optimized analysis conditions. These samples were diluted to a minimum volume and introduced to the ICP-MS via low flow (40-100 microL/min) microconcentric nebulizers. SRM 966 L1 was also analyzed directly, but results were highly variable. The ID-ICP-MS sample preparation and ratio measurement protocols described here resulted in total expanded uncertainties of less than 1% for the determination of 90.85 microg kg(-1) Cd in SRM 3240, and less than 10% total expanded uncertainty for the determination of 0.0468 microg kg(-1) Cd in SRM 1598a.

An optimized chronology for a stalagmite using seasonal trace element cycles from Shihua Cave, Beijing, North China

NASA Astrophysics Data System (ADS)

Ban, F.; Baker, A.; Marjo, C.; Duan, W.; Li, X.; Coleborn, K.; Akter, R.; Nagra, G.

2017-12-01

Stalagmites play an increasingly important role in the paleoclimatic reconstruction from seasonal to orbital timescales. One of the important reasons is that 230Th-dating can provide an absolute age enabling more accurate knowledge of the stalagmite growth. Additionally, annual trace element and optical layers can provide complementary method for determining a precise age and seasonal resolution. The trace elements of a stalagmite (XMG) in Beijing Shihua Cave, which is located in the East Asian monsoon region, were analyzed by laser ablation ICP-MS and compared with stalagmite laminae. The results show that: (1) the polished section of the topmost 4 mm of stalagmite XMG has obvious bi-optical layers (fluorescence and visible light) under a conventional transmission microscope. In the rest of the sample laminae are not observed using this method. (2) The variations of P/Ca, Sr/Ca, Ba/Ca, U/Ca and Mg/Ca show seasonal cycles throughout the sample. Sr/Ca is inversely correlated to P/Ca, and its peaks correspond with the (non-fluorescing) white layers, which deposit in late winter and spring when the climate is dry. The peaks of P/Ca match closely with the (fluorescing) opaque layers, because P is a soil-derived element which increases in the high rainfall monsoon period. (3) The PCA of the five trace elements showed that the cycles of PC1 could represent the annual cycle. This stalagmite was deposited over 148 ± 4 years through peak counting and the cycles of PC1 correspond well with the annual layers. Trace element cyclicity as shown by PC1 can increase the accuracy of stalagmite dating, especially in the absence of obvious laminae. The trace elements can be used as the marker of seasonal changes in a strongly contrasting wet-dry monsoon climate regime. Keywords: high-precision dating; LA-ICP-MS; stalagmite; trace elements; seasonal cycles; Shihua Cave

Mercury and trace element distribution in density separates of a South African Highveld (#4) coal: Implications for mercury reduction and preparation of export coal

USGS Publications Warehouse

Kolker, Allan; Senior, Connie L.; van Alphen, Chris; Koenig, Alan E.; Geboy, Nicholas J.

2017-01-01

Eight density separates of Permian Highveld (#4) coal were investigated for partitioning of Hg and trace elements. The separates include float fractions obtained in heavy media having densities of 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0 g/cm3, and the sink fraction for 2.0 g/cm3. Bulk analysis of the separates shows strong (R2 ≥ 0.80) positive correlations between pyritic sulfur and mercury, and between ash yield and both pyritic sulfur and mercury. Laser ablation (LA) ICP-MS analysis of individual pyrite grains in the separates confirms association of Hg and As with pyrite as indicated by bulk analysis. Other elements detected in pyrite by LA-ICP-MS include Mn, Co, Ni, Tl, and Pb. Results for the separates allow prediction of Hg, trace elements, and ash yields expected in specific South African coal products. These range from 0.06 ppm Hg and an ash yield of 11.5% ash for the export fraction to 0.47 ppm Hg and an ash yield of 60.9% for the discard (stone) fraction (dry basis). Results show pronounced differences expected between coal used for domestic power generation and coal which is exported.

Speciation and Localization of Arsenic in White and Brown Rice Grains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meharg, Andrew A.; Lombi, Enzo; Williams, Paul N.

2008-06-30

Synchrotron-based X-ray fluorescence (S-XRF) was utilized to locate arsenic (As) in polished (white) and unpolished (brown) rice grains from the United States, China, and Bangladesh. In white rice As was generally dispersed throughout the grain, the bulk of which constitutes the endosperm. In brown rice As was found to be preferentially localized at the surface, in the region corresponding to the pericarp and aleurone layer. Copper, iron, manganese, and zinc localization followed that of arsenic in brown rice, while the location for cadmium and nickel was distinctly different, showing relatively even distribution throughout the endosperm. The localization of As inmore » the outer grain of brown rice was confirmed by laser ablation ICP?MS. Arsenic speciation of all grains using spatially resolved X-ray absorption near edge structure (?-XANES) and bulk extraction followed by anion exchange HPLC?ICP?MS revealed the presence of mainly inorganic As and dimethylarsinic acid (DMA). However, the two techniques indicated different proportions of inorganic:organic As species. A wider survey of whole grain speciation of white (n = 39) and brown (n = 45) rice samples from numerous sources (field collected, supermarket survey, and pot trials) showed that brown rice had a higher proportion of inorganic arsenic present than white rice. Furthermore, the percentage of DMA present in the grain increased along with total grain arsenic.« less

Magnesium content within the skeletal architecture of the coral Montastraea faveolata: locations of brucite precipitation and implications to fine-scale data fluctuations

USGS Publications Warehouse

Buster, N.A.; Holmes, C.W.

2006-01-01

Small portions of coral cores were analyzed using a high-resolution laser ablation inductively coupled plasma mass spectrometer (LA ICP-MS) to determine the geochemical signatures within and among specific skeletal structures in the large framework coral, Montastraea faveolata. Vertical transects were sampled along three parallel skeletal structures: endothecal (septal flank), corallite wall, and exothecal (costal flank) areas. The results demonstrate that trace element levels varied among the three structures. Magnesium (Mg) varied among adjacent structures and was most abundant within the exothecal portion of the skeleton. Scanning electron microscopy (SEM) revealed the presence of hexagonal crystals forming thick discs, pairs or doublets of individual crystals, and rosettes in several samples. High Mg within these crystals was confirmed with energy dispersive spectroscopy (EDS), infrared spectrometry, and LA ICP-MS. The chemical composition is consistent with the mineral brucite [Mg(OH2)]. These crystals are located exclusively in the exothecal area of the skeleton, are often associated with green endolithic algae, and are commonly associated with increased Mg levels found in the adjacent corallite walls. Although scattered throughout the exothecal, the brucite crystals are concentrated within green bands where levels of Mg increase substantially relative to other portions of the skeleton. The presence and locations of high-Mg crystals may explain the fine-scale fluctuations in Mg data researchers have been questioning for years.

A multimodal imaging workflow to visualize metal mixtures in the human placenta and explore colocalization with biological response markers.

PubMed

Niedzwiecki, Megan M; Austin, Christine; Remark, Romain; Merad, Miriam; Gnjatic, Sacha; Estrada-Gutierrez, Guadalupe; Espejel-Nuñez, Aurora; Borboa-Olivares, Hector; Guzman-Huerta, Mario; Wright, Rosalind J; Wright, Robert O; Arora, Manish

2016-04-01

Fetal exposure to essential and toxic metals can influence life-long health trajectories. The placenta regulates chemical transmission from maternal circulation to the fetus and itself exhibits a complex response to environmental stressors. The placenta can thus be a useful matrix to monitor metal exposures and stress responses in utero, but strategies to explore the biologic effects of metal mixtures in this organ are not well-developed. In this proof-of-concept study, we used laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to measure the distributions of multiple metals in placental tissue from a low-birth-weight pregnancy, and we developed an approach to identify the components of metal mixtures that colocalized with biological response markers. Our novel workflow, which includes custom-developed software tools and algorithms for spatial outlier identification and background subtraction in multidimensional elemental image stacks, enables rapid image processing and seamless integration of data from elemental imaging and immunohistochemistry. Using quantitative spatial statistics, we identified distinct patterns of metal accumulation at sites of inflammation. Broadly, our multiplexed approach can be used to explore the mechanisms mediating complex metal exposures and biologic responses within placentae and other tissue types. Our LA-ICP-MS image processing workflow can be accessed through our interactive R Shiny application 'shinyImaging', which is available at or through our laboratory's website, .

LA-ICP-MS trace element mapping: insights into the crystallisation history of a metamorphic garnet population

NASA Astrophysics Data System (ADS)

George, Freya; Gaidies, Fred

2017-04-01

In comparison to our understanding of major element zoning, relatively little is known about the incorporation of trace elements into metamorphic garnet. Given their extremely slow diffusivities and sensitivity to changing mineral assemblages, the analysis of the distribution of trace elements in garnet has the potential to yield a wealth of information pertaining to interfacial attachment mechanisms during garnet crystallisation, the mobility of trace elements in both garnet and the matrix, and trace element geochronology. Due to advances in the spatial resolution and analytical precision of modern microbeam techniques, small-scale trace element variations can increasingly be documented and used to inform models of metamorphic crystallisation. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) in particular, can be used to rapidly quantify a wide range of elemental masses as a series of laser rasters, producing large volumes of spatially constrained trace element data. In this study, we present LA-ICP-MS maps of trace element concentrations from numerous centrally-sectioned garnets representative of the crystal size-distribution of a single sample's population. The study sample originates from the garnet-grade Barrovian zone of the Lesser Himalayan Sequence in Sikkim, northeast India, and has been shown to have crystallised garnet within a single assemblage between 515 ˚C and 565˚C, with no evidence for accessory phase reaction over the duration of garnet growth. Previous models have indicated that the duration of garnet crystallisation was extremely rapid (<1 Myr), with negligible diffusional homogenisation of major divalent cations. Consequently, the trace element record likely documents the primary zonation generated during garnet growth. In spite of straightforward (i.e. concentrically-zoned) major element garnet zonation, trace elements maps are characterised by significant complexity and variability. Y and the heavy rare earth elements are strongly enriched in crystal cores, where there is overprinting of the observed internal fabric, and exhibit numerous concentric annuli towards crystal rims. Conversely, the medium rare earth elements (e.g. Gd, Eu and Sm) exhibit bowl-shaped zoning from core to rim, with no annuli, and core and rim compositions of the medium rare earth elements are the same throughout the population within crystals of differing size. Cr exhibits pronounced spiral zoning, and the average Cr content increases towards garnet rims. In all cases, spirals are centered on the geometric core of the crystals. These LA-ICP-MS maps highlight the complexity of garnet growth over a single prograde event, and indicate that there is still much to be learnt from the analysis of garnet using ever-improving analytical methods. We explore the potential causes of the variations in the distribution of trace elements in garnet, and assess how these zoning patterns may be used to refine our understanding of the intricacies of garnet crystallisation and the spatial and temporal degree of trace element equilibration during metamorphism.

Cellular processing of gold nanoparticles: CE-ICP-MS evidence for the speciation changes in human cytosol.

PubMed

Legat, Joanna; Matczuk, Magdalena; Timerbaev, Andrei R; Jarosz, Maciej

2018-01-01

The cellular uptake of gold nanoparticles (AuNPs) may (or may not) affect their speciation, but information on the chemical forms in which the particles exist in the cell remains obscure. An analytical method based on the use of capillary electrophoresis hyphenated with inductively coupled plasma mass spectrometry (ICP-MS) has been proposed to shed light on the intracellular processing of AuNPs. It was observed that when being introduced into normal cytosol, the conjugates of 10-50 nm AuNPs with albumin evolved in human serum stayed intact. On the contrary, under simulated cancer cytosol conditions, the nanoconjugates underwent decomposition, the rate of which and the resulting metal speciation patterns were strongly influenced by particle size. The new peaks that appeared in ICP-MS electropherograms could be ascribed to nanosized species, as upon ultracentrifugation, they quantitatively precipitated whereas the supernatant showed only trace Au signals. Our present study is the first step to unravel a mystery of the cellular chemistry for metal-based nanomedicines.

Chromium in rivers impacted by tannery wastes determined by high performance liquid chromatography - inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Pereira de Abreu, M.-H.; Vignati, D.; Dominik, J.

2003-05-01

The total chromium concentrations by ICP-MS and HPLC-ICP-MS and the redox chromium species have been determined in rivers impacted by untreated wastes from tanneries at Fès (Morocco). The results obtained by two ICP-MS analysis methods showed significantly different chromium values at m/z 53. The higher values obtained with external calibration, can be attributed to matrix effects, especially ^{37}Cl ^{16}O at m/z 53. This is confirmed on the chromatograms by the presence of a peak at 100s with the anomalous ^{52}Cr/^{53}Cr isotopic ratio. The hexavalent chromium was not detected. Two trivalent chromium monomer species, Cr(OH)(H2O)5^{2+} and Cr(H2O)6^{3+}, were present in low concentrations. We suppose that the major part of chromium occurred as Cr(III) polymeric species which were not retained on the column. These Cr(III) forms are usually complexed with Cl^- or/and SO4^{2-}, used as tanning agents.

Specific determination of bromate in bread by ion chromatography with ICP-MS.

PubMed

Akiyama, Takumi; Yamanaka, Michiko; Date, Yukiko; Kubota, Hiroki; Nagaoka, Megumi Hamano; Kawasaki, Yoko; Yamazaki, Takeshi; Yomota, Chikako; Maitani, Tamio

2002-12-01

A sensitive method for detecting bromate in bread by ion chromatography with inductively-coupled plasma mass spectrometry (IC/ICP-MS) was developed. Bromate was extracted from bread with water. The clean-up procedure included a 0.2 micron filter, a C18 cartridge for defatting, a silver cartridge to remove halogen anions, a centrifugal ultrafiltration unit to remove proteins, and a cation-exchange cartridge to remove silver ions. A 500 microL sample solution was applied to IC/ICP-MS. The detection limit and the quantitation limit of bromate in the solution were 0.3 ng/mL and 1.0 ng/mL, expressed as HBrO3, respectively, which corresponded to 2 ng/g and 5 ng/g, respectively, in bread. Recovery of bromate was about 90%, and the CV was about 2%. Based on the detection limit in solution and recovery from bread, the detection limit of bromate in bread was estimated to be 2 ng/g.

Metabolomic and elemental analysis of camel and bovine urine by GC-MS and ICP-MS.

PubMed

Ahamad, Syed Rizwan; Alhaider, Abdul Qader; Raish, Mohammad; Shakeel, Faiyaz

2017-01-01

Recent studies from the author's laboratory indicated that camel urine possesses antiplatelet activity and anti-cancer activity which is not present in bovine urine. The objective of this study is to compare the volatile and elemental components of bovine and camel urine using GC-MS and ICP-MS analysis. We are interested to know the component that performs these biological activities. The freeze dried urine was dissolved in dichloromethane and then derivatization process followed by using BSTFA for GC-MS analysis. Thirty different compounds were analyzed by the derivatization process in full scan mode. For ICP-MS analysis twenty eight important elements were analyzed in both bovine and camel urine. The results of GC-MS and ICP-MS analysis showed marked difference in the urinary metabolites. GC-MS evaluation of camel urine finds a lot of products of metabolism like benzene propanoic acid derivatives, fatty acid derivatives, amino acid derivatives, sugars, prostaglandins and canavanine. Several research reports reveal the metabolomics studies on camel urine but none of them completely reported the pharmacology related metabolomics. The present data of GC-MS suggest and support the previous studies and activities related to camel urine.

Quantitative Evaluation of Cisplatin Uptake in Sensitive and Resistant Individual Cells by Single-Cell ICP-MS (SC-ICP-MS).

PubMed

Corte Rodríguez, M; Álvarez-Fernández García, R; Blanco, E; Bettmer, J; Montes-Bayón, M

2017-11-07

One of the main limitations to the Pt-therapy in cancer is the development of associated drug resistance that can be associated with a significant reduction of the intracellular platinum concentration. Thus, intracellular Pt concentration could be considered as a biomarker of cisplatin resistance. In this work, an alternative method to address intracellular Pt concentration in individual cells is explored to permit the evaluation of different cell models and alternative therapies in a relatively fast way. For this aim, total Pt analysis in single cells has been implemented using a total consumption nebulizer coupled to inductively coupled plasma mass spectrometric detection (ICP-MS). The efficiency of the proposed device has been evaluated in combination with flow cytometry and turned out to be around 25% (cells entering the ICP-MS from the cells in suspension). Quantitative uptake studies of a nontoxic Tb-containing compound by individual cells were conducted and the results compared to those obtained by bulk analysis of the same cells. Both sets of data were statistically comparable. Thus, final application of the developed methodology to the comparative uptake of Pt-species in cisplatin resistant and sensitive cell lines (A2780cis and A2780) was conducted. The results obtained revealed the potential of this analytical strategy to differentiate between different cell lines of different sensitivity to the drug which might be of high medical interest.

A multifunctional probe for ICP-MS determination and multimodal imaging of cancer cells.

PubMed

Yang, Bin; Zhang, Yuan; Chen, Beibei; He, Man; Yin, Xiao; Wang, Han; Li, Xiaoting; Hu, Bin

2017-10-15

Inductively coupled plasma-mass spectrometry (ICP-MS) based bioassay and multimodal imaging have attracted increasing attention in the current development of cancer research and theranostics. Herein, a sensitive, simple, timesaving, and reliable immunoassay for cancer cells counting and dual-modal imaging was proposed by using ICP-MS detection and down-conversion fluorescence (FL)/upconversion luminescence (UCL) with the aid of a multifunctional probe for the first time. The probe consisted of a recognition unit of goat anti-mouse IgG to label the anti-EpCAM antibody attached cells, a fluorescent dye (Cy3) moiety for FL imaging as well as upconversion nanoparticles (UCNPs) tag for both ICP-MS quantification and UCL imaging of cancer cells. Under the optimized conditions, an excellent linearity and sensitivity were achieved owing to the signal amplification effect of nanoparticles and low spectral interference. Accordingly, a limit of detection (3σ) of 1×10 2 HepG2 cells and a relative standard deviation of 7.1% for seven replicate determinations of 1×10 3 HepG2 cells were obtained. This work proposed a method to employ UCNPs with highly integrated functionalities enabling us not only to count but also to see the cancer cells, opening a promising avenue for biological research and clinical theranostics. Copyright © 2017 Elsevier B.V. All rights reserved.

Simultaneous detection of MCF-7 and HepG2 cells in blood by ICP-MS with gold nanoparticles and quantum dots as elemental tags.

PubMed

Li, Xiaoting; Chen, Beibei; He, Man; Wang, Han; Xiao, Guangyang; Yang, Bin; Hu, Bin

2017-04-15

In this work, we demonstrate a novel method based on inductively coupled plasma mass spectrometry (ICP-MS) detection with gold nanoparticles (Au NPs) and quantum dots (QDs) labeling for the simultaneous counting of two circulating tumor cell lines (MCF-7 and HepG2 cells) in human blood. MCF-7 and HepG2 cells were captured by magnetic beads coupled with anti-EpCAM and then specifically labeled by CdSe QDs-anti-ASGPR and Au NPs-anti-MUC1, respectively, which were used as signal probes for ICP-MS measurement. Under the optimal experimental conditions, the limits of detection of 50 MCF-7, 89 HepG2 cells and the linear ranges of 200-40000 MCF-7, 300-30000 HepG2 cells were obtained, and the relative standard deviations for seven replicate detections of 800 MCF-7 and HepG2 cells were 4.6% and 5.7%, respectively. This method has the advantages of high sensitivity, low sample consumption, wide linear range and can be extended to the simultaneous detection of multiple CTC lines in human peripheral blood. Copyright © 2016 Elsevier B.V. All rights reserved.

Chip-based magnetic solid phase microextraction coupled with ICP-MS for the determination of Cd and Se in HepG2 cells incubated with CdSe quantum dots.

PubMed

Yu, Xiaoxiao; Chen, Beibei; He, Man; Wang, Han; Hu, Bin

2018-03-01

The quantification of trace Cd and Se in cells incubated with CdSe quantum dots (QDs) is critical to investigate the cytotoxicity of CdSe QDs. In this work, a miniaturized platform, namely chip-based magnetic solid phase microextraction (MSPME) packing with sulfhydryl group functionalized magnetic nanoparticles, was fabricated and combined with inductively coupled plasma mass spectrometry (ICP-MS) for the determination of trace Cd and Se in cells. Under the optimized conditions, the limits of detection (LOD) of the developed chip-based MSPME-ICP-MS system are 2.2 and 21ngL -1 for Cd and Se, respectively. The proposed method is applied successfully to the analysis of total and released small molecular fraction of Cd and Se in Human hepatocellular carcinoma cells (HepG2 cells) incubated with CdSe QDs, and the recoveries for the spiked samples are in the range of 86.0-109%. This method shows great promise to analyze cell samples and the obtained results are instructive to explore the cytotoxicity mechanism of CdSe QDs in cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Gold nanoparticle labeling with tyramide signal amplification for highly sensitive detection of alpha fetoprotein in human serum by ICP-MS.

PubMed

Li, Xiaoting; Chen, Beibei; He, Man; Xiao, Guangyang; Hu, Bin

2018-01-01

In this work, we developed an immunoassay based on tyramide signal amplification (TSA) and gold nanoparticles (Au NPs) labeling for highly sensitive detection of alpha fetoprotein (AFP) by inductively coupled plasma mass spectrometry (ICP-MS). AFP was captured by anti-AFP1 coating on the 96-well plate and labeled by anti-AFP2-horseradish peroxidase (HRP), in which the HRP can catalyze the deposition of biotinylated tyramine on the nearby protein. Then the streptavidin (SA)-Au NPs was labeled on the deposited biotinylated tyramine as the intensive signal probe for ICP-MS measurement. Under the optimal experimental conditions, the limit of detection of the developed method for AFP was 1.85pg/mL and the linear range was 0.005-2ng/mL. The relative standard deviation for seven replicate detections of 0.01ng/mL AFP was 5.2%. The proposed method was successfully applied to the detection of AFP in human serum with good recoveries. This strategy is highly sensitive and easy to operate, and can be extended to the sensitive detection of other biomolecules in human serum. Copyright © 2017 Elsevier B.V. All rights reserved.

Determination of trace-level haloacetic acids in drinking water by ion chromatography-inductively coupled plasma mass spectrometry.

PubMed

Liu, Yongjian; Mou, Shifen; Chen, Dengyun

2004-06-11

A new method for the determination of nine haloacetic acids (HAAs) with ion chromatography (IC) coupled to inductively coupled plasma mass spectrometry (ICP-MS) was developed. With the very hydrophilic anion-exchange column and steep gradient of sodium hydroxide, the nine HAAs could be well separated in 15 min. After suppression with an ASRS suppressor that was introduced in between IC and ICP-MS, the background was much decreased, the interference caused by sodium ion present in eluent was removed, and the sensitivities of HAAs were greatly improved. The chlorinated and brominated HAAs could be detected as 35ClO and 79Br without interference of the matrix due to the elemental selective ICP-MS. The detection limits for mono-, di-, trichloroacetic acids were between 15.6 and 23.6 microg/l. For the other six bromine-containing HAAs, the detection limits were between 0.34 and 0.99 microg/l. With the pretreatment of OnGuard Ag cartridge to remove high concentration of chloride in sample, the developed method could be applied to the determination of HAAs in many drinking water matrices.

Analysis of Rare Earth Elements in Geologic Samples using Inductively Coupled Plasma Mass Spectrometry; US DOE Topical Report - DOE/NETL-2016/1794

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bank, Tracy L.; Roth, Elliot A.; Tinker, Phillip

2016-04-17

Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is used to measure the concentrations of rare earth elements (REE) in certified standard reference materials including shale and coal. The instrument used in this study is a Perkin Elmer Nexion 300D ICP-MS. The goal of the study is to identify sample preparation and operating conditions that optimized recovery of each element of concern. Additionally, the precision and accuracy of the technique are summarized and the drawbacks and limitations of the method are outlined.

Development, validation and application of an ICP-MS/MS method to quantify minerals and (ultra-)trace elements in human serum.

PubMed

Meyer, Sören; Markova, Mariya; Pohl, Gabriele; Marschall, Talke A; Pivovarova, Olga; Pfeiffer, Andreas F H; Schwerdtle, Tanja

2018-09-01

Multi-element determination in human samples is very challenging. Especially in human intervention studies sample volumes are often limited to a few microliters and due to the high number of samples a high-throughput is indispensable. Here, we present a state-of-the-art ICP-MS/MS-based method for the analysis of essential (trace) elements, namely Mg, Ca, Fe, Cu, Zn, Mo, Se and I, as well as food-relevant toxic elements such as As and Cd. The developed method was validated regarding linearity of the calibration curves, method LODs and LOQs, selectivity and trueness as well as precision. The established reliable method was applied to quantify the element serum concentrations of participants of a human intervention study (LeguAN). The participants received isocaloric diets, either rich in plant protein or in animal protein. While the serum concentrations of Mg and Mo increased in participants receiving the plant protein-based diet (above all legumes), the Se concentration in serum decreased. In contrast, the animal protein-based diet, rich in meat and dairy products, resulted in an increased Se concentration in serum. Copyright © 2018 Elsevier GmbH. All rights reserved.

A validated inductively coupled plasma mass spectrometry (ICP-MS) method for the quantification of total platinum content in plasma, plasma ultrafiltrate, urine and peritoneal fluid.

PubMed

Lemoine, Lieselotte; Thijssen, Elsy; Noben, Jean-Paul; Adriaensens, Peter; Carleer, Robert; Speeten, Kurt Van der

2018-04-15

Oxaliplatin is a platinum (Pt) 1 containing antineoplastic agent that is applied in current clinical practice for the treatment of colon and appendiceal neoplasms. A fully validated, highly sensitive, high throughput inductively coupled plasma mass spectrometry (ICP-MS) method is provided to quantify the total Pt content in plasma, plasma ultrafiltrate, urine and peritoneal fluid. In this ICP-MS approach, the only step of sample preparation is a 1000-fold dilution in 0.5% nitric acid, allowing the analysis of 17 samples per hour. Detection of Pt was achieved over a linear range of 0.01-100 ng/mL. The limit of quantification was 18.0 ng/mL Pt in plasma, 8.0 ng/mL in ultrafiltrate and 6.1 ng/mL in urine and peritoneal fluid. The ICP-MS method was further validated for inter-and intraday precision and accuracy (≤15%), recovery, robustness and stability. Short-term storage of the biofluids, for 14 days, can be performed at -4 °C, -24 °C and -80 °C. As to long-term stability, up to 5 months, storage at -80 °C is encouraged. Furthermore, a timeline assessing the total and unbound Pt fraction in plasma and ultrafiltrate over a period of 45 h is provided. Following an incubation period of 5 h at 37 °C, 19-21% of Pt was recovered in the ultrafiltrate, emphasizing the extensive and rapid binding of oxaliplatin-derived Pt to plasma proteins. The described method can easily be implemented in a routine setting for pharmacokinetic studies in patients treated with oxaliplatin-based hyperthermic intraperitoneal perioperative chemotherapy. Copyright © 2018 Elsevier B.V. All rights reserved.

Interlaboratory evaluation of trace element determination in workplace air filter samples by inductively coupled plasma mass spectrometry†‡

PubMed Central

Shulman, Stanley A.; Brisson, Michael J.; Howe, Alan M.

2015-01-01

Inductively coupled plasma mass spectrometry (ICP-MS) is becoming more widely used for trace elemental analysis in the occupational hygiene field, and consequently new ICP-MS international standard procedures have been promulgated by ASTM International and ISO. However, there is a dearth of interlaboratory performance data for this analytical methodology. In an effort to fill this data void, an interlaboratory evaluation of ICP-MS for determining trace elements in workplace air samples was conducted, towards fulfillment of method validation requirements for international voluntary consensus standard test methods. The study was performed in accordance with applicable statistical procedures for investigating interlaboratory precision. The evaluation was carried out using certified 37-mm diameter mixed-cellulose ester (MCE) filters that were fortified with 21 elements of concern in occupational hygiene. Elements were spiked at levels ranging from 0.025 to 10 μg filter−1, with three different filter loadings denoted “Low”, “Medium” and “High”. Participating laboratories were recruited from a pool of over fifty invitees; ultimately twenty laboratories from Europe, North America and Asia submitted results. Triplicates of each certified filter with elemental contents at three different levels, plus media blanks spiked with reagent, were conveyed to each volunteer laboratory. Each participant was also provided a copy of the test method which each participant was asked to follow; spiking levels were unknown to the participants. The laboratories were requested to prepare the filters by one of three sample preparation procedures, i.e., hotplate digestion, microwave digestion or hot block extraction, which were described in the test method. Participants were then asked to analyze aliquots of the prepared samples by ICP-MS, and to report their data in units of μg filter−1. Most interlaboratory precision estimates were acceptable for medium- and high-level spikes (RSD <25%), but generally yielded greater uncertainties than were anticipated at the outset of the study. PMID:22038017

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

PubMed

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

2008-04-01

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

Implementation of ICP-MS protocols for uranium urinary measurements in worker monitoring.

PubMed

Baglan, N; Cossonnet, C; Trompier, F; Ritt, J; Bérard, P

1999-10-01

The uranium concentration in human urine spiked with natural uranium and rat urine containing metabolized depleted uranium was determined by ICP-MS. The use of ICP-MS was investigated without any chemical treatment or after the different stages of a purification protocol currently carried out for routine monitoring. In the case of spiked urine, the measured uranium concentrations were consistent with those certified by an intercomparison network in radiotoxicological analysis (PROCORAD) and with those obtained by alpha spectrometry in the case of the urine containing metabolized uranium. The quantitative information which could be obtained in the different protocols investigated shows the extent to which ICP-MS provides greater flexibility for setting up appropriate monitoring approaches in radiation protection routines and accidental situations. This is due to the combination of high sensitivity and the accuracy with which traces of uranium in urine can be determined in a shorter time period. Moreover, it has been shown that ICP-MS measurement can be used to quantify the 235U isotope, which is useful for characterizing the nature of the uranium compound, but difficult to perform using alpha spectrometry.

Efficient analysis of complex natural materials using LA-ICP-MS

NASA Astrophysics Data System (ADS)

Kent, A. J.; Loewen, M. W.; Koleszar, A. M.; Miller, J.; Ungerer, C. "

2011-12-01

Many natural materials exhibit complex variations in chemical or isotopic composition over relatively short length scales, and these compositional variations often record important information about the environment or nature of the processes that lead to formation. Examples include complexly zoned crystals within volcanic rocks that record magmatic and volcanic signals, otoliths and other biominerals that record life history and environmental information, and speleothems that record climatic variables. Laser ablation ICP-MS analyses offer several advantages for quantifying compositional in chemically complex natural materials. These include the speed of analysis, the ability to sample at atmospheric pressures, the wide diversity of possible analytes, and the ability to make measurements in both spot and raster modes. The latter in particular offers advantages for analyses that require efficient acquisition of information over significant length scales, as in raster mode compositional data can be rapidly obtained by translating the laser laterally over a compositional variable material during a single analysis. In this fashion elemental or isotopic composition at a given analysis time corresponds to the lateral spatial dimension. This contrasts with a record obtained by a row of individual spots, which require a large number of discrete analyses, and requires significantly more analysis time. However there are also disadvantages to this style of analysis. Translation of the circular spots typically used for analysis results in significant signal attenuation and production of artifacts that may mirror natural diffusion profiles or other gradual changes. The ability to ablate using non-circular spots significantly reduces this effect, although the degree of attenuation is also increased by slower ablation cell response times. For single volume cells this may result in 50-100% additional attenuation than that produced by the translation of the spot alone, although two-volume and other rapid response cells significantly reduce this effect. Raster analyses are also highly sensitive to the presence of small contaminant phases along the raster trajectory, as the compositional signal from these can become attenuated and difficult to distinguish from natural compositional variations. It can also be difficult to establish exactly where compositional changes occur in materials that are visually homogenous. In this contribution we discuss these issues in more detail and present data acquisition and processing strategies that minimize these difficulties.

Subduction / exhumation dynamics: Petrochronology in the Glacier-Rafray slice (Western Alps, Italy)

NASA Astrophysics Data System (ADS)

Burn, Marco; Lanari, Pierre; Engi, Martin

2014-05-01

Petrochronology is the combination of in situ age-dating, geothermobarometry and structural geology and aims to unravel Pressure-Temperature-deformation-time (P-T-ɛ-t) paths. To link P-T conditions to deformation stages is daily business for metamorphic petrologists, but recent micro-mapping techniques (XMapTools program) provide an additional tool to achieve this goal. Absolute age is often difficult to assess in metamorphic rocks, as it is challenging to link specific P-T conditions to most of the mineral chronometers. Allanite is a common accessory phase in high-P metamorphic rocks and is a potential target to determine Th(-U)/Pb ages. Allanite from a leucocratic gneiss of the Glacier-Rafray slice in the western Alps consists of several chemically different zones: one major zone can be linked to a first high-P phengite generation. To determine the age of this high-P growth zone we used La-ICP-MS in situ techniques, which allowed us to date an appropriate growth rim per grain. Even so particular care was required when evaluating the isotope signals laser ablation leads to the excavation of a volume, which potentially can be chemically and/or age-zoned. We have developed a new method to track changes in the plasma during the ablation. This method aims to identify discrete age zones. La-ICP-MS spectra have been modeled so as to reproduce the shape of the spectra measured. These results indicate that high-P allanite first grew in equilibrium with phengite at 84 ± 4 Ma, whereas a second growth event occurred at ~40 Ma. A final epidotic rim grew at greenschist facies conditions, but this stage could not be dated. These findings have implications for our interpretation of several units in the Western Alps: In the Sesia Zone (former Adriatic margin), the earliest high-P metamorphism occurred at 85 Ma (Regis et al., 2014), precisely as the first high-P peak we discovered in the Glacier-Rafray slice. Austroalpine klippen such as this are commonly seen as extensional allochthons; one would expect these to have entered the subduction zone together with the Piemonte oceanic units. Yet all high-P ages reported for the Piemonte oceanic units are around 40 Ma. We propose that the Glacier-Rafray slice experienced subduction together with Sesia units and may have been juxtaposed on the Piemont-Ligurian-Ocean units during Eocene exhumation. Strain associated with this juxtaposition may have triggered growth of the second allanite. Joint exhumation of the oceanic units and the Glacier-Rafray klippe followed at retrograde T.

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

PubMed

Yang, Lu

2009-01-01

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

Development of a certified reference material (NMIJ CRM 7531-a) for the determination of trace cadmium and other elements in brown rice flour.

PubMed

Miyashita, Shin-ichi; Inagaki, Kazumi; Narukawa, Tomohiro; Zhu, Yanbei; Kuroiwa, Takayoshi; Hioki, Akiharu; Chiba, Koichi

2012-01-01

A certified reference material (CRM) for trace cadmium and other elements in brown rice flour was developed at the National Metrology Institute of Japan (NMIJ). The CRM was provided as a dry powder after drying and frozen pulverization of fresh brown rice obtained from a Japanese domestic market. Characterization of the property value for each element was carried out exclusively by NMIJ with at least two independent analytical methods, including inductively coupled plasma mass spectrometry (ICP-MS), ICP high-resolution mass spectrometry, isotope-dilution ICP-MS, ICP optical emission spectrometry, and graphite-furnace atomic-absorption spectrometry. Property values were provided for six elements (Mn, Fe, Cu, Zn, As, and Cd). The concentration range of the property values was from 0.280 mg kg(-1) of As to 31.8 mg kg(-1) of Zn. The combined relative standard uncertainties of the property values were estimated by considering the uncertainties of the homogeneity, characterization, difference among analytical methods, dry-mass correction factor, and calibration standard. The range of the relative combined standard uncertainties was from 1.1% of Zn to 1.6% of As.

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; preparation procedure for aquatic biological material determined for trace metals

USGS Publications Warehouse

Hoffman, Gerald L.

1996-01-01

A method for the chemical preparation of tissue samples that are subsequently analyzed for 22 trace metals is described. The tissue-preparation procedure was tested with three National Institute of Standards and Technology biological standard reference materials and two National Water Quality Laboratory homogenized biological materials. A low-temperature (85 degrees Celsius) nitric acid digestion followed by the careful addition of hydrogen peroxide (30-percent solution) is used to decompose the biological material. The solutions are evaporated to incipient dryness, reconstituted with 5 percent nitric acid, and filtered. After filtration the solutions were diluted to a known volume and analyzed by inductively coupled plasma-mass spectrometry (ICP-MS), inductively coupled plasma-atomic emission spectrometry (ICP-AES), and cold vapor-atomic absorption spectrophotometry (CV-AAS). Many of the metals were determined by both ICP-MS and ICP-AES. This report does not provide a detailed description of the instrumental procedures and conditions used with the three types of instrumentation for the quantitation of trace metals determined in this study. Statistical data regarding recovery, accuracy, and precision for individual trace metals determined in the biological material tested are summarized.

Subcellular analysis by laser ablation electrospray ionization mass spectrometry

DOEpatents

Vertes, Akos; Stolee, Jessica A; Shrestha, Bindesh

2014-12-02

In various embodiments, a method of laser ablation electrospray ionization mass spectrometry (LAESI-MS) may generally comprise micro-dissecting a cell comprising at least one of a cell wall and a cell membrane to expose at least one subcellular component therein, ablating the at least one subcellular component by an infrared laser pulse to form an ablation plume, intercepting the ablation plume by an electrospray plume to form ions, and detecting the ions by mass spectrometry.

Method of low tantalum amounts determination in niobium and its compounds by ICP-OES technique.

PubMed

Smolik, Marek; Turkowska, Magdalena

2013-10-15

A method of determination of low amounts of tantalum in niobium and niobium compounds without its prior separation by means of inductively coupled plasma optical emission spectrometry (ICP-OES) has been worked out. The method involves dissolution of the analyzed samples of niobium as well as its various compounds (oxides, fluorides, chlorides, niobates(V)) in fluoride environments, precipitation of sparingly soluble niobic(tantalic) acid (Nb2O5(Ta2O5) · xH2O), converting them into soluble complex compounds by means of oxalic acid with addition of hydrogen peroxide and finally analyzing directly obtained solutions by ICP-OES. This method permits determination of Ta in niobium at the level of 10(-3)% with relatively good precision (≤ 8% RSD) and accuracy (recovery factor: 0.9-1.1). Relative differences in the results obtained by two independent methods (ICP-OES and ICP-MS) do not exceed 14%, and other elements present in niobium compounds (Ti, W, Zr, Hf, V, Mo, Fe, Cr) at the level of 10(-2)% do not affect determination. © 2013 Elsevier B.V. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sullivan, Patrick Allen

2005-12-17

Quantification in liquid chromatography (LC) is becoming very important as more researchers are using LC, not as an analytical tool itself, but as a sample introduction system for other analytical instruments. The ability of LC instrumentation to quickly separate a wide variety of compounds makes it ideal for analysis of complex mixtures. For elemental speciation, LC is joined with inductively coupled plasma mass spectrometry (ICP-MS) to separate and detect metal-containing, organic compounds in complex mixtures, such as biological samples. Often, the solvent gradients required to perform complex separations will cause matrix effects within the plasma. This limits the sensitivity ofmore » the ICP-MS and the quantification methods available for use in such analyses. Traditionally, isotope dilution has been the method of choice for LC-ICP-MS quantification. The use of naturally abundant isotopes of a single element in quantification corrects for most of the effects that LC solvent gradients produce within the plasma. However, not all elements of interest in speciation studies have multiple naturally occurring isotopes; and polyatomic interferences for a given isotope can develop within the plasma, depending on the solvent matrix. This is the case for reverse phase LC separations, where increasing amounts of organic solvent are required. For such separations, an alternative to isotope dilution for quantification would be is needed. To this end, a new method was developed using the Apex-Q desolvation system (ESI, Omaha, NE) to couple LC instrumentation with an ICP-MS device. The desolvation power of the system allowed greater concentrations of methanol to be introduced to the plasma prior to destabilization than with direct methanol injection into the plasma. Studies were performed, using simulated and actual linear methanol gradients, to find analyte-internal standard (AIS) pairs whose ratio remains consistent (deviations {+-} 10%) over methanol concentration ranges of 5%-35% (simulated) and 8%-32% (actual). Quadrupole (low resolution) and sector field (high resolution) ICP-MS instrumentation were utilized in these studies. Once an AIS pair is determined, quantification studies can be performed. First, an analysis is performed by adding both elements of the AIS pair post-column while performing the gradient elution without sample injection. A comparison of the ratio of the measured intensities to the atomic ratio of the two standards is used to determine a correction factor that can be used to account for the matrix effects caused by the mobile phase. Then, organic and/or biological molecules containing one of the two elements in the AIS pair are injected into the LC column. A gradient method is used to vary the methanol-water mixture in the mobile phase and to separate out the compounds in a given sample. A standard solution of the second ion in the AIS pair is added continuously post-column. By comparing the ratio of the measured intensities to the atomic ratio of the eluting compound and internal standard, the concentration of the injected compound can be determined.« less

Determination of As, Cd, Hg and Pb in continuous use drugs and excipients by plasma-based techniques in compliance with the United States Pharmacopeia requirements

NASA Astrophysics Data System (ADS)

da Silva, Caroline Santos; Pinheiro, Fernanda Costa; do Amaral, Clarice Dias Britto; Nóbrega, Joaquim Araújo

2017-12-01

Some inorganic impurities are toxic to human health even when present at low concentrations and therefore must be carefully monitored in products as continuous use drugs. This work aimed the development of a simple microwave-assisted digestion procedure for different types of drugs and excipients and the analytical determination of elemental impurities according to the new regulations of the United States Pharmacopeia (USP) 232 and 233 using inductively coupled plasma optical emission spectrometry (ICP-OES) or inductively coupled plasma mass spectrometry (ICP-MS). Eight drugs samples and two excipients of different brands were microwave-assisted digested with inverse aqua regia. Addition and recovery experiments were performed according to J values, once permissible daily exposure value is specific for each element and estimated according to the maximum daily dose of drug indicated by the label. Samples were spiked with values of 1.5J in order to check accuracies for As, Cd, Hg, and Pb. Recoveries obtained by ICP-OES ranged from 75 to 148% and for ICP-MS ranged from 74 to 120%. The limits of detection for ICP-OES ranged from 0.4 to 17 mg kg- 1 and for ICP-MS from 7.4 to 41.6 μg kg- 1. Both analytical methods were adequate in terms of accuracies and sensitivities. Considering the maximum daily dose, all drugs samples and excipients contained As, Cd, Hg and Pb below the maximum limits stipulated by USP since all of them presented contents below respective limits of detection.

Study of the use of axial viewed inductively coupled plasma atomic emission spectrometry with ultrasonic nebulization for the determination of select elemental impurities in oral drug products.

PubMed

Menoutis, James; Parisi, Angela; Verma, Natasha

2018-04-15

In efforts to control the potential presence of heavy metals in pharmaceuticals, the United States Pharmacopeia (USP) and International Conference on Harmonization (ICH) have put forth new requirements and guidelines for their control. The new requirements and guidelines establish specific daily exposures (PDE) for 24 heavy metals/elemental impurities (EI) based upon their toxicological properties. USP General Chapter 〈233〉 provides a general reference procedure for preparing pharmaceutical samples for analysis employing microwave assisted digestion (MWAD). It also provides two Compendial Procedures, Procedure 1 employing ICP-AES, and Procedure 2 employing ICP-MS. Given the extremely low detection limits afforded by ICP-MS, much work has been done in developing and evaluating analytical methods to support the analysis of elemental impurities in finished pharmaceutical products, active pharmaceutical ingredients, and excipients by this analytical technique. In this study, we have evaluated the use of axial ICP-AES. This employs ultrasonic nebulization (UN) for the determination of Class 1 and 2 EI, instead of traditional pneumatic nebulization. The study also employed closed vessel MWAD to prepare samples for analysis. Limits of quantitation were element specific and significantly lower than the PDEs for oral drugs. Spike recoveries for the elements studied ranged between 89.3% and 109.25%, except for Os, which was subject to OsO4 formation during MWAD. The use of axial ICP-AES UN provides an alternative to ICP-MS in the analysis of EI requiring low detection limits. Copyright © 2018 Elsevier B.V. All rights reserved.

Trace element contamination in feather and tissue samples from Anna’s hummingbirds

USGS Publications Warehouse

Mikoni, Nicole A.; Poppenga, Robert H.; Ackerman, Joshua T.; Foley, Janet E.; Hazlehurst, Jenny; Purdin, Güthrum; Aston, Linda; Hargrave, Sabine; Jelks, Karen; Tell, Lisa A.

2017-01-01

Trace element contamination (17 elements; Be, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Ba, Hg, Tl, and Pb) of live (feather samples only) and deceased (feather and tissue samples) Anna's hummingbirds (Calypte anna) was evaluated. Samples were analyzed using inductively coupled plasma-mass spectrometry (ICP-MS; 17 elements) and atomic absorption spectrophotometry (Hg only). Mean plus one standard deviation (SD) was considered the benchmark, and concentrations above the mean + 1 SD were considered elevated above normal. Contour feathers were sampled from live birds of varying age, sex, and California locations. In order to reduce thermal impacts, minimal feathers were taken from live birds, therefore a novel method was developed for preparation of low mass feather samples for ICP-MS analysis. The study found that the novel feather preparation method enabled small mass feather samples to be analyzed for trace elements using ICP-MS. For feather samples from live birds, all trace elements, with the exception of beryllium, had concentrations above the mean + 1 SD. Important risk factors for elevated trace element concentrations in feathers of live birds were age for iron, zinc, and arsenic, and location for iron, manganese, zinc, and selenium. For samples from deceased birds, ICP-MS results from body and tail feathers were correlated for Fe, Zn, and Pb, and feather concentrations were correlated with renal (Fe, Zn, Pb) or hepatic (Hg) tissue concentrations. Results for AA spectrophotometry analyzed samples from deceased birds further supported the ICP-MS findings where a strong correlation between mercury concentrations in feather and tissue (pectoral muscle) samples was found. These study results support that sampling feathers from live free-ranging hummingbirds might be a useful, non-lethal sampling method for evaluating trace element exposure and provides a sampling alternative since their small body size limits traditional sampling of blood and tissues. The results from this study provide a benchmark for the distribution of trace element concentrations in feather and tissue samples from hummingbirds and suggests a reference mark for exceeding normal. Lastly, pollinating avian species are minimally represented in the literature as bioindicators for environmental trace element contamination. Given that trace elements can move through food chains by a variety of routes, our study indicates that hummingbirds are possible bioindicators of environmental trace element contamination.

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; determination of whole-water recoverable arsenic, boron, and vanadium using inductively coupled plasma-mass spectrometry

USGS Publications Warehouse

Garbarino, John R.

2000-01-01

Analysis of in-bottle digestate by using the inductively coupled plasma?mass spectrometric (ICP?MS) method has been expanded to include arsenic, boron, and vanadium. Whole-water samples are digested by using either the hydrochloric acid in-bottle digestion procedure or the nitric acid in-bottle digestion procedure. When the hydrochloric acid in-bottle digestion procedure is used, chloride must be removed from the digestate by subboiling evaporation before arsenic and vanadium can be accurately determined. Method detection limits for these elements are now 10 to 100 times lower than U.S. Geological Survey (USGS) methods using hydride generation? atomic absorption spectrophotometry (HG? AAS) and inductively coupled plasma? atomic emission spectrometry (ICP?AES), thus providing lower variability at ambient concentrations. The bias and variability of the methods were determined by using results from spike recoveries, standard reference materials, and validation samples. Spike recoveries in reagent-water, surface-water, ground-water, and whole-water recoverable matrices averaged 90 percent for seven replicates; spike recoveries were biased from 25 to 35 percent low for the ground-water matrix because of the abnormally high iron concentration. Results for reference material were within one standard deviation of the most probable value. There was no significant difference between the results from ICP?MS and HG?AAS or ICP?AES methods for the natural whole-water samples that were analyzed.

Radial line-scans as representative sampling strategy in dried-droplet laser ablation of liquid samples deposited on pre-cut filter paper disks

NASA Astrophysics Data System (ADS)

Nischkauer, Winfried; Vanhaecke, Frank; Bernacchi, Sébastien; Herwig, Christoph; Limbeck, Andreas

2014-11-01

Nebulising liquid samples and using the aerosol thus obtained for further analysis is the standard method in many current analytical techniques, also with inductively coupled plasma (ICP)-based devices. With such a set-up, quantification via external calibration is usually straightforward for samples with aqueous or close-to-aqueous matrix composition. However, there is a variety of more complex samples. Such samples can be found in medical, biological, technological and industrial contexts and can range from body fluids, like blood or urine, to fuel additives or fermentation broths. Specialized nebulizer systems or careful digestion and dilution are required to tackle such demanding sample matrices. One alternative approach is to convert the liquid into a dried solid and to use laser ablation for sample introduction. Up to now, this approach required the application of internal standards or matrix-adjusted calibration due to matrix effects. In this contribution, we show a way to circumvent these matrix effects while using simple external calibration for quantification. The principle of representative sampling that we propose uses radial line-scans across the dried residue. This compensates for centro-symmetric inhomogeneities typically observed in dried spots. The effectiveness of the proposed sampling strategy is exemplified via the determination of phosphorus in biochemical fermentation media. However, the universal viability of the presented measurement protocol is postulated. Detection limits using laser ablation-ICP-optical emission spectrometry were in the order of 40 μg mL- 1 with a reproducibility of 10 % relative standard deviation (n = 4, concentration = 10 times the quantification limit). The reported sensitivity is fit-for-purpose in the biochemical context described here, but could be improved using ICP-mass spectrometry, if future analytical tasks would require it. Trueness of the proposed method was investigated by cross-validation with conventional liquid measurements, and by analyzing IAEA-153 reference material (Trace Elements in Milk Powder); a good agreement with the certified value for phosphorus was obtained.

Reduction of iodate in iodated salt to iodide during cooking with iodine as measured by an improved HPLC/ICP-MS method.

PubMed

Liu, Liejun; Li, Xiuwei; Wang, Haiyan; Cao, Xiaoxiao; Ma, Wei

2017-04-01

Iodate is a strong oxidant, and some animal studies indicate that iodate intake may cause adverse effects. A key focus of the safety assessment of potassium iodate as a salt additive is determining whether iodate is safely reduced to iodide in food. To study the reduction of iodate in table salt to iodide and molecular iodine during cooking. Fifteen food samples cooked with and without iodated salt were prepared in duplicate. The iodine in the cooked food was extracted with deionized water. The iodine species in the extracts were determined by using an improved high-performance liquid chromatography/inductively coupled plasma-mass spectrometry (HPLC/ICP-MS). The cooking temperature and the pH of the food were determined. The conversion rate of iodate in iodated salt to iodide and molecular iodine was 96.4%±14.7% during cooking, with 86.8%±14.5% of the iodate converted to iodide ions and 9.6% ±6.2% converted to molecular iodine to lose. The limit of detection, limit of quantification, relative standard deviation and recovery rate of the method HPLC/ICP-MS were 0.70 μg/L for I - (0.69 μg/L for IO 3 - ), 2.10 μg/L for I - (2.06 μg/L for IO 3 - ), 2.6% and 101.6%±2.6%, respectively. Almost all iodate added to food was converted into iodide and molecular iodine during cooking. The improved HPLC/ICP-MS was reliable in the determination of iodine species in food extracts. Copyright © 2017 Elsevier Inc. All rights reserved.

The potential of inductively coupled plasma mass spectrometry (ICP-MS) for the simultaneous determination of trace elements in whole blood, plasma and serum.

PubMed

Krachler, M; Irgolic, K J

1999-11-01

The advantages accruing to biochemical and clinical investigations from a method that allows the simultaneous quantification (RSD < or = 10%) of many elements in blood, plasma, and serum at concentrations equal to one-hundredth of the lower limits of the normal ranges are undeniable. The suitability of inductively coupled argon plasma low-resolution quadrupole mass spectrometry (ICP-MS), a simultaneous method with low detection limits, is evaluated for the quantification of inorganic constituents in whole blood, plasma, and serum with consideration of the dilution associated with the mineralization of the samples, of isobaric and polyatomic interferences and of normal ranges. Of the 3 bulk elements, the 3 major electrolytes, the 15 essential elements, the 8 toxic elements, the 4 therapeutic elements, and the 14 elements of potential interest (total of 47 elements) only 7 elements (Ca, Cu, K, Mg, Rb, Sr, Zn) can be simultaneously quantified under these rigorous conditions in serum and only 8 elements (additional element Pb) in whole blood. Quantification of elements in the Seronorm Standards "Whole Blood" and "Serum" showed, that this list of simultaneously determinable elements in these matrices is reasonable. Although this list is disappointingly short, the number of elements determinable simultaneously by ICP-MS is still larger than that by ICP-AES or GFAAS. Improved detectors, more efficient nebulizers, avoidance of interferences, better instrument design, and high-resolution mass spectrometers promise to increase the number of elements that can be determined simultaneously.

LC coupled to ESI, MALDI and ICP MS - A multiple hyphenation for metalloproteomic studies.

PubMed

Coufalíková, Kateřina; Benešová, Iva; Vaculovič, Tomáš; Kanický, Viktor; Preisler, Jan

2017-05-22

A new multiple detection arrangement for liquid chromatography (LC) that supplements conventional electrospray ionization (ESI) mass spectrometry (MS) detection with two complementary detection techniques, matrix-assisted laser desorption/ionization (MALDI) MS and substrate-assisted laser desorption inductively coupled plasma (SALD ICP) MS has been developed. The combination of the molecular and elemental detectors in a single separation run is accomplished by utilizing a commercial MALDI target made of conductive plastic. The proposed platform provides a number of benefits in today's metalloproteomic applications, which are demonstrated by analysis of a metallothionein mixture. To maintain metallothionein complexes, separation is carried out at a neutral pH. The effluent is split; a major portion is directed to ESI MS while the remaining 1.8% fraction is deposited onto a plastic MALDI target. Dried droplets are overlaid with MALDI matrix and analysed consecutively by MALDI MS and SALD ICP MS. In the ESI MS spectra, the MT isoform complexes with metals and their stoichiometry are determined; the apoforms are revealed in the MALDI MS spectra. Quantitative determination of metallothionein isoforms is performed via determination of metals in the complexes of the individual protein isoforms using SALD ICP MS. Copyright © 2017 Elsevier B.V. All rights reserved.

Preparation And Analysis Of Specimens Of Ablative Materials

NASA Technical Reports Server (NTRS)

Solomon, William C.

1994-01-01

Procedure for chemical analysis of specimens of silicone-based ablative thermal-insulation materials SLA-561 and MA25 involves acid digestion of specimens to prepare them for analysis by inductively-coupled-plasma/atomic-emission spectroscopy (ICP/AES). In comparison with atomic-absorption spectroscopy (AAS), ICP/AES is faster and more accurate than AAS. Results of analyses stored in data base, used to trace variations in concentrations of chemical elements in materials during long-term storage, and used in timely manner in investigations of failures. Acid-digestion portion of procedure applied to other thermal-insulation materials containing room-temperature-vulcanizing silicones and enables instrumental analysis of these materials.

Concerns about Quadrupole ICP-MS Lead Isotopic Data and Interpretations in the Environment and Health Fields.

PubMed

Gulson, Brian; Kamenov, George D; Manton, William; Rabinowitz, Michael

2018-04-11

There has been a massive increase in recent years of the use of lead (Pb) isotopes in attempts to better understand sources and pathways of Pb in the environment and in man or experimental animals. Unfortunately, there have been many cases where the quality of the isotopic data, especially that obtained by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS), are questionable, resulting in questionable identification of potential sources, which, in turn, impacts study interpretation and conclusions. We present several cases where the isotopic data have compromised interpretation because of the use of only the major isotopes 208 Pb/ 206 Pb and 207 Pb/ 206 Pb, or their graphing in other combinations. We also present some examples comparing high precision data from thermal ionization (TIMS) or multi-collector plasma mass spectrometry (MC-ICP-MS) to illustrate the deficiency in the Q-ICP-MS data. In addition, we present cases where Pb isotopic ratios measured on Q-ICP-MS are virtually impossible for terrestrial samples. We also evaluate the Pb isotopic data for rat studies, which had concluded that Pb isotopic fractionation occurs between different organs and suggest that this notion of biological fractionation of Pb as an explanation for isotopic differences is not valid. Overall, the brief review of these case studies shows that Q-ICP-MS as commonly practiced is not a suitable technique for precise and accurate Pb isotopic analysis in the environment and health fields.

Concerns about Quadrupole ICP-MS Lead Isotopic Data and Interpretations in the Environment and Health Fields

PubMed Central

Gulson, Brian; Manton, William; Rabinowitz, Michael

2018-01-01

There has been a massive increase in recent years of the use of lead (Pb) isotopes in attempts to better understand sources and pathways of Pb in the environment and in man or experimental animals. Unfortunately, there have been many cases where the quality of the isotopic data, especially that obtained by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS), are questionable, resulting in questionable identification of potential sources, which, in turn, impacts study interpretation and conclusions. We present several cases where the isotopic data have compromised interpretation because of the use of only the major isotopes 208Pb/206Pb and 207Pb/206Pb, or their graphing in other combinations. We also present some examples comparing high precision data from thermal ionization (TIMS) or multi-collector plasma mass spectrometry (MC-ICP-MS) to illustrate the deficiency in the Q-ICP-MS data. In addition, we present cases where Pb isotopic ratios measured on Q-ICP-MS are virtually impossible for terrestrial samples. We also evaluate the Pb isotopic data for rat studies, which had concluded that Pb isotopic fractionation occurs between different organs and suggest that this notion of biological fractionation of Pb as an explanation for isotopic differences is not valid. Overall, the brief review of these case studies shows that Q-ICP-MS as commonly practiced is not a suitable technique for precise and accurate Pb isotopic analysis in the environment and health fields. PMID:29641487

Study of the chemical composition of particulate matter from the Rio de Janeiro metropolitan region, Brazil, by inductively coupled plasma-mass spectrometry and optical emission spectrometry

NASA Astrophysics Data System (ADS)

Mateus, Vinícius Lionel; Monteiro, Isabela Luizi Gonçalves; Rocha, Rafael Christian Chávez; Saint'Pierre, Tatiana Dillenburg; Gioda, Adriana

2013-08-01

Air quality in the metropolitan region of Rio de Janeiro was evaluated by analysis of particulate matter (PM) in industrial (Santa Cruz) and rural (Seropédica) areas. Total suspended particles (TSP) and fine particulate matter (PM2.5) collected in filters over 24 h were quantified and their chemical composition determined. TSP exceeded Brazilian guidelines (80 μg m- 3) in Santa Cruz, while PM2.5 levels exceeded the World Health Organization guidelines (10 μg m- 3) in both locations. Filters were extracted with water and/or HNO3, and the concentrations of 20 elements, mostly metals, were determined by inductively coupled plasma mass spectrometry (ICP-MS) and optical emission spectrometry (ICP OES). Water soluble inorganic anions were determined by ion chromatography (IC). To estimate the proportion of these elements extracted, a certified reference material (NIST SRM 1648a, Urban Dust) was subjected to the same extraction process. Concordant results were obtained by ICP-MS and ICP OES for most elements. Some elements could not be quantified by both techniques; the most appropriate technique was chosen in each case. The urban dust was also analyzed by the United States Environmental Protection Agency (US EPA) method, which employs a combination of hydrochloric and nitric acids for the extraction, but higher extraction efficiency was obtained when only nitric acid was employed. The US EPA method gave better results only for Sb. In the PM samples, the elements found in the highest average concentrations by ICP were Zn and Al (3-6 μg m- 3). The anions found in the highest average concentrations were SO42 - in PM2.5 (2-4 μg m- 3) and Cl- in TSP (2-6 μg m- 3). Principal component analysis (PCA) in combination with enrichment factors (EF) indicated industrial sources in PM2.5. Analysis of TSP suggested both anthropogenic and natural sources. In conclusion, this work contributes data on air quality, as well as a method for the analysis of PM samples by ICP-MS.

Analysis of twenty five impurities in uranium matrix by ICP-MS with iron measurement optimized by using reaction collision cell, cold plasma or medium resolution.

PubMed

Quemet, Alexandre; Brennetot, Rene; Chevalier, Emilie; Prian, Edwina; Laridon, Anne-Laure; Mariet, Clarisse; Fichet, Pascal; Laszak, Ivan; Goutelard, Florence

2012-09-15

An analytical procedure was developed to determine the concentration of 25 impurities (Li, Be, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ag, Cd, In, Sm, Eu, Gd, Dy, W, Pb, Bi and Th) in a uranium matrix using the quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS). The dissolution of U(3)O(8) powder was made with a mixture of hydrochloric acid and nitric acid. Then, a selective separation of uranium using the UTEVA column was used before measurement by Q-ICP-MS. The procedure developed was verified using the Certified Reference Material "Morille". The analytical results agree well except for 5 elements where values are underestimated (Li, Be, In, Pb and Bi). Among the list of impurities, iron was particularly investigated because it is well known that this element possesses a polyatomic interference that increases the detection limit. A comparison between iron detection limits obtained with different methods was performed. Iron polyatomic interference was at least reduced, or at best entirely resolved in some cases, by using the cold plasma or the collision/reaction cell with several gases (He, NH(3) and CH(4)). High-resolution ICP-MS was used to compare the results obtained. A detection limit as low as 8 ng L(-1) was achieved. Copyright © 2012 Elsevier B.V. All rights reserved.

Analysis of IAEA Environmental Samples for Plutonium and Uranium by ICP/MS in Support Of International Safeguards

DOE Office of Scientific and Technical Information (OSTI.GOV)

Farmer, Orville T.; Olsen, Khris B.; Thomas, May-Lin P.

2008-05-01

A method for the separation and determination of total and isotopic uranium and plutonium by ICP-MS was developed for IAEA samples on cellulose-based media. Preparation of the IAEA samples involved a series of redox chemistries and separations using TRU® resin (Eichrom). The sample introduction system, an APEX nebulizer (Elemental Scientific, Inc), provided enhanced nebulization for a several-fold increase in sensitivity and reduction in background. Application of mass bias (ALPHA) correction factors greatly improved the precision of the data. By combining the enhancements of chemical separation, instrumentation and data processing, detection levels for uranium and plutonium approached high attogram levels.

Selected isotope ratio measurements of light metallic elements (Li, Mg, Ca, and Cu) by multiple collector ICP-MS

PubMed Central

Platzner, Thomas I.; Segal, Irina

2007-01-01

The unique capabilities of multiple collector inductively coupled mass spectrometry (MC-ICP-MS) for high precision isotope ratio measurements in light elements as Li, Mg, Ca, and Cu are reviewed in this paper. These elements have been intensively studied at the Geological Survey of Israel (GSI) and other laboratories over the past few years, and the methods used to obtain high precision isotope analyses are discussed in detail. The scientific study of isotopic fractionation of these elements is significant for achieving a better understanding of geochemical and biochemical processes in nature and the environment. PMID:17962922

The Means: Cytometry and Mass Spectrometry Converge in a Single Cell Deep Profiling Platform

PubMed Central

Weis-Garcia, Frances; Bandura, Dmitry; Baranov, Vladimir; Ornatsky, Olga; Tanner, Scott

2013-01-01

Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is a distinct flavor of mass spectrometry that has had little association with cell biology: it remains the state of the art for the determination of the atomic composition of materials. Unrelatedly, flow cytometry is the superior method for distinguishing the heterogeneity of cells through the determination of antigen signatures using tagged antibodies. Simply replacing fluorophore tags with stable isotopes of the heavy metals, and measuring these cell-by-cell with ICP-MS, dramatically increases the number of probes that can be simultaneously measured in cytometry and enables a transformative increase in the resolution of rare cell populations in complex biological samples. While this can be thought of as a novel incarnation of single-cell targeted proteomics, the metal-labeling reagents, ICP-MS of single cells, and accompanying informatics comprise a new field of technology termed Mass Cytometry. While the conception of mass cytometry is simple the embodiment to address the issues of multi-parameter flow cytometry has been far more challenging. There are many elements, and many more stable isotopes of those elements, that might be used as distinct reporter tags. Still, there are many approaches to conjugating metals to antibodies (or other affinity reagents) and work in this area along with developing new applications is ongoing. The mass resolution and linear (quantitative) dynamic range of ICP-MS allows those many stable isotopes to be measured simultaneously and without the spectral overlap issues that limit fluorescence assay. However, the adaptation of ICP-MS to allow high-speed simultaneous measurement with single cell distinction at high throughput required innovation of the cell introduction system, ion optics (sampling, transmission and beam-shaping), mass analysis, and signal handling and processing. An overview of “the nuts and bolts” of Mass Cytometry is presented.

Validation of an isotope dilution, ICP-MS method based on internal mass bias correction for the determination of trace concentrations of Hg in sediment cores.

PubMed

Ciceri, E; Recchia, S; Dossi, C; Yang, L; Sturgeon, R E

2008-01-15

The development and validation of a method for the determination of mercury in sediments using a sector field inductively coupled plasma mass spectrometer (SF-ICP-MS) for detection is described. The utilization of isotope dilution (ID) calibration is shown to solve analytical problems related to matrix composition. Mass bias is corrected using an internal mass bias correction technique, validated against the traditional standard bracketing method. The overall analytical protocol is validated against NRCC PACS-2 marine sediment CRM. The estimated limit of detection is 12ng/g. The proposed procedure was applied to the analysis of a real sediment core sampled to a depth of 160m in Lake Como, where Hg concentrations ranged from 66 to 750ng/g.

An improved method for total organic iodine in drinking water.

PubMed

Sayess, Rassil; Reckhow, David A

2017-01-01

A concise, rapid, and sensitive method is developed to measure organically-bound iodine in water. Total organic iodine (TOI) is used as an integrative surrogate that reflects the amount of iodinated organics in a water sample and is quantified using a refined method that builds on previous adsorption and detection approaches. The proposed method combines adsorption, combustion, and trapping of combustion products, with an offline inductively coupled plasma/mass spectrometer (ICP-MS) for iodide detection. During method development, three analytical variables (factors) were varied across two levels each in order to optimize the method for iodine recovery: 1) the sample pH prior to adsorption on the granular activated carbon (GAC); 2) the amount of base addition to the trap solution; and 3) composition of the ICP-MS wash solution. These factors were tested with solutions of eight iodinated model organic compounds, two iodinated inorganic compounds, and field water samples using a full factorial experimental design. An analysis of variance (ANOVA) and related statistical methods were deployed to identify the best combination of conditions (i.e., treatment) that results in the most complete recovery of iodine from the model compounds and the highest rejection of inorganic iodine. The chosen treatment for TOI measurement incorporates a sample pH of less than 1 prior to adsorption onto the GAC, a solution of 2% (v/v) tetramethyl ammonium hydroxide (TMAH) for trapping of combustion products, and a TMAH wash solution of 0.1% (v/v) for the ICP-MS. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

A table of polyatomic interferences in ICP-MS

USGS Publications Warehouse

May, Thomas W.; Wiedmeyer, Ray H.

1998-01-01

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

Potentialities of mass spectrometry (ICP-MS) for actinides determination in urine.

PubMed

Bouvier-Capely, C; Ritt, J; Baglan, N; Cossonnet, C

2004-05-01

The applicability of inductively coupled plasma-mass spectrometry (ICP-MS) for determining actinides in urine was investigated. Performances of ICP-MS including detection limit and analysis time were studied and compared with alpha spectrometry performances. In the field of individual monitoring of workers, the comparison chart obtained in this study can be used as a guide for medical laboratories to select the most adequate procedure to be carried out depending on the case in question (the radioisotope to be measured, the required sensitivity, and the desired response time).

Fast Determination of Toxic Arsenic Species in Food Samples Using Narrow-bore High-Performance Liquid-Chromatography Inductively Coupled Plasma Mass Spectrometry.

PubMed

Terol, Amanda; Marcinkowska, Monika; Ardini, Francisco; Grotti, Marco

2016-01-01

A new method for the speciation analysis of arsenic in food using narrow-bore high-performance liquid-chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS) has been developed. Fast separation of arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid was carried out in 7 min using an anion-exchange narrow-bore Nucleosil 100 SB column and 12 mM ammonium dihydrogen phosphate of pH 5.2 as the mobile phase, at a flow rate of 0.3 mL min(-1). A PFA-ST micronebulizer jointed to a cyclonic spray chamber was used for HPLC-ICP-MS coupling. Compared with standard-bore HPLC-ICP-MS, the new method has provided higher sensitivity, reduced mobile-phase consumption, a lower matrix plasma load and a shorter analysis time. The achieved instrumental limits of detection were in the 0.3 - 0.4 ng As mL(-1) range, and the precision was better than 3%. The arsenic compounds were efficiently (>80%) extracted from various food samples using a 1:5 methanol/water solution, with additional ultrasonic treatment for rice products. The applicability of this method was demonstrated by the analysis of several samples, such as seafood (fish, mussels, shrimps, edible algae) and rice-based products (Jasmine and Arborio rice, spaghetti, flour, crackers), including three certified reference materials.

Enantioselective determination of the organochlorine pesticide bromocyclen in spiked fish tissue using solid-phase microextraction coupled to gas chromatography with ECD and ICP-MS detection.

PubMed

Fidalgo-Used, Natalia; Montes-Bayón, Maria; Blanco-González, Elisa; Sanz-Medel, Alfredo

2008-05-15

A method for enantioselective determination of bromocyclen enantiomers in fish tissue has been developed. The enantiomers were resolved by capillary gas chromatography (GC) using a commercial chiral column (CP-Chirasil-Dex CB) and a temperature program from 50 degrees C (held for 1 min), raised to 140 degrees C at 40 degrees C min(-1) and then raised at 0.2 degrees C min(-1) to 155 degrees C. This enantioselective gas chromatographic separation was combined with a clean-up/enrichment procedure based on solid-phase microextraction (SPME). Under SPME optimized conditions, precision, linearity range and detection limits of the developed SPME-enantioselective GC procedure were evaluated and compared using two different detection systems: a classical electron-capture detection (ECD) and an element specific detection using inductively coupled plasma mass spectrometry (ICP-MS). The SPME-GC-ECD method exhibited an excellent sensitivity, with detection limits of 0.2 ng L(-1) for each enantiomer of bromocyclen. Although ICP-MS offered poorer detection limits (7 ng L(-1) as Br, equivalent to 36 ng L(-1) of each enantiomer) than conventional ECD detector, it proved to be clearly superior in terms of selectivity. The relative potential and performance of the two compared methods for real-life analysis has been illustrated by the determination of enantiomers of bromocyclen in spiked tissue extracts of trout.

Inductively Coupled Plasma Optical Emission Spectrometry for Rare Earth Elements Analysis

NASA Astrophysics Data System (ADS)

He, Man; Hu, Bin; Chen, Beibei; Jiang, Zucheng

2017-01-01

Inductively coupled plasma optical emission spectrometry (ICP-OES) merits multielements capability, high sensitivity, good reproducibility, low matrix effect and wide dynamic linear range for rare earth elements (REEs) analysis. But the spectral interference in trace REEs analysis by ICP-OES is a serious problem due to the complicated emission spectra of REEs, which demands some correction technology including interference factor method, derivative spectrum, Kalman filtering algorithm and partial least-squares (PLS) method. Matrix-matching calibration, internal standard, correction factor and sample dilution are usually employed to overcome or decrease the matrix effect. Coupled with various sample introduction techniques, the analytical performance of ICP-OES for REEs analysis would be improved. Compared with conventional pneumatic nebulization (PN), acid effect and matrix effect are decreased to some extent in flow injection ICP-OES, with higher tolerable matrix concentration and better reproducibility. By using electrothermal vaporization as sample introduction system, direct analysis of solid samples by ICP-OES is achieved and the vaporization behavior of refractory REEs with high boiling point, which can easily form involatile carbides in the graphite tube, could be improved by using chemical modifier, such as polytetrafluoroethylene and 1-phenyl-3-methyl-4-benzoyl-5-pyrazone. Laser ablation-ICP-OES is suitable for the analysis of both conductive and nonconductive solid samples, with the absolute detection limit of ng-pg level and extremely low sample consumption (0.2 % of that in conventional PN introduction). ICP-OES has been extensively employed for trace REEs analysis in high-purity materials, and environmental and biological samples.

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

PubMed

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

2014-09-02

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

Determination of ultra-low level plutonium isotopes (239Pu, 240Pu) in environmental samples with high uranium.

PubMed

Xing, Shan; Zhang, Weichao; Qiao, Jixin; Hou, Xiaolin

2018-09-01

In order to measure trace plutonium and its isotopes ratio ( 240 Pu/ 239 Pu) in environmental samples with a high uranium, an analytical method was developed using radiochemical separation for separation of plutonium from matrix and interfering elements including most of uranium and ICP-MS for measurement of plutonium isotopes. A novel measurement method was established for extensively removing the isobaric interference from uranium ( 238 U 1 H and 238 UH 2 + ) and tailing of 238 U, but significantly improving the measurement sensitivity of plutonium isotopes by employing NH 3 /He as collision/reaction cell gases and MS/MS system in the triple quadrupole ICP-MS instrument. The results show that removal efficiency of uranium interference was improved by more than 15 times, and the sensitivity of plutonium isotopes was increased by a factor of more than 3 compared to the conventional ICP-MS. The mechanism on the effective suppress of 238 U interference for 239 Pu measurement using NH 3 -He reaction gases was explored to be the formation of UNH + and UNH 2 + in the reactions of UH + and U + with NH 3 , while no reaction between NH 3 and Pu + . The detection limits of this method were estimated to be 0.55 fg mL -1 for 239 Pu, 0.09 fg mL -1 for 240 Pu. The analytical precision and accuracy of the method for Pu isotopes concentration and 240 Pu/ 239 Pu atomic ratio were evaluated by analysis of sediment reference materials (IAEA-385 and IAEA-412) with different levels of plutonium and uranium. The developed method were successfully applied to determine 239 Pu and 240 Pu concentrations and 240 Pu/ 239 Pu atomic ratios in soil samples collected in coastal areas of eastern China. Copyright © 2018 Elsevier B.V. All rights reserved.

Microfluidic high performance liquid chromatography-chip hyphenation to inductively coupled plasma-mass spectrometry.

PubMed

Bishop, David P; Blanes, Lucas; Wilson, Alexander B; Wilbanks, Thor; Killeen, Kevin; Grimm, Rudolf; Wenzel, Ross; Major, Derek; Macka, Mirek; Clarke, David; Schmid, Robin; Cole, Nerida; Doble, Philip A

2017-05-12

The Agilent Chip Cube Interface is a microfluidic chip-based technology originally designed for nanospray molecular mass spectrometry in which the sample enrichment, nano-column, tubing, connectors and spray tip were integrated into a single biocompatible chip. Here we describe the hyphenation of the Chip Cube Interface to ICP-MS via modification of the standard HPLC chip design and a new total consumption nebuliser suitable for flow rates as low as 300nLmin -1 . The potential of the instrument to eliminate common nanoLC - ICP-MS shortcomings such as leaks, blockages and band-broadening was demonstrated via analysis of cyanocobalamin in equine plasma. The method was linear over three orders of magnitude with an r 2 of 0.9999, the peak area repeatability was 1.9% (n=7), and the detection limit was 14ngmL -1 . This novel configuration of the Chip Cube Interface coupled to ICP-MS is a suitable platform for the analysis of biomolecules associated with trace metals and speciation applications. Copyright © 2017 Elsevier B.V. All rights reserved.

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

PubMed

Hirata, Shizuko; Toshimitsu, Hideki

2005-10-01

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

Hybridation of different chiral separation techniques with ICP-MS detection for the separation and determination of selenomethionine enantiomers: chiral speciation of selenized yeast.

PubMed

Méndez, S P; González, E B; Sanz-Medel, A

2001-05-01

Enantioseparation and determination of selenomethionine enantiomers in selenized yeast was investigated using chiral separation techniques based on different principles, coupled on-line to inductively coupled plasma mass spectrometry (ICP-MS) for selenium-specific detection. High performance liquid chromatography (HPLC) on a beta-cyclodestrin (beta-CD) column, cyclodextrin-modified micellar electrokinetic chromatography (CD-MEKC), gas chromatography (GC) on a Chirasil-L-Val column, and HPLC on a Chirobiotic T column have been investigated as the chiral separation techniques. For HPLC separation on the beta-CD column, and also for CD-MEKC, selenomethionine enantiomers were derivatized with NDA/CN(-). For chiral separation by GC, selenomethionine enantiomers were converted into their N-trifluoroacetyl (TFA)-O-alkyl esters. The developed hybridation methodologies are compared with respect to enantioselectivity, sensitivity and analysis time. The usefulness of the best-suited method [HPLC (Chirobiotic T)-ICP-MS] was demonstrated by its application to the successful chiral speciation of selenium and D-and L-selenomethionine content determination in selenized yeast. Copyright 2001 John Wiley & Sons, Ltd.

Quantification of 60Fe atoms by MC-ICP-MS for the redetermination of the half-life.

PubMed

Kivel, Niko; Schumann, Dorothea; Günther-Leopold, Ines

2013-03-01

In many scientific fields, the half-life of radionuclides plays an important role. The accurate knowledge of this parameter has direct impact on, e.g., age determination of archeological artifacts and of the elemental synthesis in the universe. In order to derive the half-life of a long-lived radionuclide, the activity and the absolute number of atoms have to be analyzed. Whereas conventional radiation measurement methods are typically applied for activity determinations, the latter can be determined with high accuracy by mass spectrometric techniques. Over the past years, the half-lives of several radionuclides have been specified by means of multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) complementary to the earlier reported values mainly derived by accelerator mass spectrometry. The present paper discusses all critical aspects (amount of material, radiochemical sample preparation, interference correction, isotope dilution mass spectrometry, calculation of measurement uncertainty) for a precise analysis of the number of atoms by MC-ICP-MS exemplified for the recently published half-life determination of 60Fe (Rugel et al, Phys Rev Lett 103:072502, 2009).

Ultra-Sensitive Elemental Analysis Using Plasmas 4.Application of Inductively Coupled Plasma Mass Spectrometry to the Study of Environmental Radioactivity

NASA Astrophysics Data System (ADS)

Yoshida, Satoshi

Applications of inductively coupled plasma mass spectrometry (ICP-MS) to the determination of long-lived radionuclides in environmental samples were summarized. In order to predict the long-term behavior of the radionuclides, related stable elements were also determined. Compared with radioactivity measurements, the ICP-MS method has advantages in terms of its simple analytical procedures, prompt measurement time, and capability of determining the isotope ratio such as240Pu/239Pu, which can not be separated by radiation. Concentration of U and Th in Japanese surface soils were determined in order to determine the background level of the natural radionuclides. The 235U/238U ratio was successfully used to detect the release of enriched U from reconversion facilities to the environment and to understand the source term. The 240Pu/239Pu ratios in environmental samples varied widely depending on the Pu sources. Applications of ICP-MS to the measurement of I and Tc isotopes were also described. The ratio between radiocesium and stable Cs is useful for judging the equilibrium of deposited radiocesium in a forest ecosystem.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoppe, Eric W.; Aalseth, Craig E.; Brodzinski, Ronald L.

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

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

USGS Publications Warehouse

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

2013-01-01

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

Quantification of Au Nanoparticle Biouptake and Distribution to Freshwater Algae Using Single Cell - ICP-MS.

PubMed

Merrifield, R C; Stephan, C; Lead, J R

2018-02-20

Quantifying metal and nanoparticle (NP) biouptake and distribution on an individual cellular basis has previously been impossible, given available techniques which provide qualitative data that are laborious to acquire and prone to artifacts. Quantifying metal and metal NP uptake and loss processes in environmental organisms will lead to mechanistic understanding of biouptake and improved understanding of potential hazards and risks of metals and NPs. In this work, we present a new technique, single cell inductively coupled plasma mass spectrometry (SC-ICP-MS), which allows quantification of metal concentrations on an individual cell basis down to the attogram (ag) per cell level. We present data validating the novel method, along with the mass of metal per cell. Finally, we use SC-ICP-MS, with ancillary cell counting methods, to quantify the biouptake and strong sorption and distribution of both dissolved Au and Au NPs in a freshwater alga (Cyptomonas ovate). The data suggests differences between dissolved and NP uptake and loss. In the case of NPs, there was a dose and time dependent uptake, but individual cellular variations; at the highest realistic exposure conditions used in this study up to 40-50% of cells contained NPs, while 50-60% of cells did not.

Metabolomics and Trace Element Analysis of Camel Tear by GC-MS and ICP-MS.

PubMed

Ahamad, Syed Rizwan; Raish, Mohammad; Yaqoob, Syed Hilal; Khan, Altaf; Shakeel, Faiyaz

2017-06-01

Camel tear metabolomics and elemental analysis are useful in getting the information regarding the components responsible for maintaining the protective system that allows living in the desert and dry regions. The aim of this study was to correlate that the camel tears can be used as artificial tears for the evaluation of dryness in the eye. Eye biomarkers of camel tears were analyzed by gas chromatography-mass spectroscopy (GC-MS) and inductively coupled plasma mass spectroscopy (ICP-MS). The major compounds detected in camel tears by GC-MS were alanine, valine, leucine, norvaline, glycine, cadaverine, urea, ribitol, sugars, and higher fatty acids like octadecanoic acid and hexadecanoic acid. GC-MS analysis of camel tears also finds several products of metabolites and its associated metabolic participants. ICP-MS analysis showed the presence of different concentration of elemental composition in the camel tears.

Messenger RNA Detection in Leukemia Cell lines by Novel Metal-Tagged in situ Hybridization using Inductively Coupled Plasma Mass Spectrometry.

PubMed

Ornatsky, Olga I; Baranov, Vladimir I; Bandura, Dmitry R; Tanner, Scott D; Dick, John

2006-01-01

Conventional gene expression profiling relies on using fluorescent detection of hybridized probes. Physical characteristics of fluorophores impose limitations on achieving a highly multiplex gene analysis of single cells. Our work demonstrates the feasibility of using metal-tagged in situ hybridization for mRNA detection by inductively coupled plasma mass spectrometry (ICP-MS). ICP-MS as an analytical detector has a number of unique and relevant properties: 1) metals and their stable isotopes generate non-overlapping distinct signals that can be detected simultaneously; 2) these signals can be measured over a wide dynamic range; 3) ICP-MS is quantitative and very sensitive. We used commercial antibodies conjugated to europium (Eu) and gold together with biotinylated oligonucleotide probes reacted with terbium-labeled streptavidin to demonstrate simultaneous mRNA and protein detection by ICP-MS in leukemia cells.

Messenger RNA Detection in Leukemia Cell lines by Novel Metal-Tagged in situ Hybridization using Inductively Coupled Plasma Mass Spectrometry

PubMed Central

Ornatsky, Olga I.; Baranov, Vladimir I.; Bandura, Dmitry R.; Tanner, Scott D.; Dick, John

2006-01-01

Conventional gene expression profiling relies on using fluorescent detection of hybridized probes. Physical characteristics of fluorophores impose limitations on achieving a highly multiplex gene analysis of single cells. Our work demonstrates the feasibility of using metal-tagged in situ hybridization for mRNA detection by inductively coupled plasma mass spectrometry (ICP-MS). ICP-MS as an analytical detector has a number of unique and relevant properties: 1) metals and their stable isotopes generate non-overlapping distinct signals that can be detected simultaneously; 2) these signals can be measured over a wide dynamic range; 3) ICP-MS is quantitative and very sensitive. We used commercial antibodies conjugated to europium (Eu) and gold together with biotinylated oligonucleotide probes reacted with terbium-labeled streptavidin to demonstrate simultaneous mRNA and protein detection by ICP-MS in leukemia cells. PMID:23662035

Database creation, data quality assessment, and geochemical maps (phase V, deliverable 59)—Final report on compilation and validation of geochemical data: Chapter D in Second projet de renforcement institutionnel du secteur minier de la République Islamique de Mauritanie (PRISM-II)

USGS Publications Warehouse

Eppinger, Robert G.; Giles, Stuart A.; Lee, Gregory K.; Smith, Steven M.

2015-01-01

The geochemical sample media collected by the BGS and BRGM under the PRISM-I contract included rock, sediment, regolith, and soil samples. Details on sample collection procedures are in unpublished reports available from PRISM. These samples were analyzed under PRISM-I contract by ALS Chemex Laboratories using various combinations of modern methods including fire-assay inductively coupled plasma-atomic emission spectrometry (ICPAES) and ICP-mass spectrometry (ICP-MS) for Au; multi-acid digestion, atomic absorption spectroscopy (AAS) for Ag and As; 47-element, four-acid digestion, ICP-MS; 27-element, fouracid digestion, ICP-AES; special four-acid ICP-MS techniques for Pt and B; fire assay followed by ICP-AES for platinum-group elements; whole-rock analyses by wavelength dispersive X-ray fluorescence (XRF); special techniques for loss-on-ignition, inorganic C, and total S; and special ore-grade AAS techniques for Ag, Au, Cu, Ni, Pb, and Zn. Around 30,000 samples were analyzed by at least one technique. However, it is stressed here that: (1) there was no common sample medium collected at all sites, likely due to the vast geological and geomorphologic differences across the country, (2) the sample site distribution is very irregular, likely due in part to access constraints and sand dune cover, and (3) there was no common across-the-board trace element analytical package used for all samples. These three aspects fundamentally affect the ability to produce country-wide geochemical maps of Mauritania. Gold (Au), silver (Ag), and arsenic (As) were the three elements that were most commonly analyzed.

Quantification of low molecular weight selenium metabolites in human plasma after treatment with selenite in pharmacological doses by LC-ICP-MS.

PubMed

Flouda, Konstantina; Dersch, Julie Maria; Gabel-Jensen, Charlotte; Stürup, Stefan; Misra, Sougat; Björnstedt, Mikael; Gammelgaard, Bente

2016-03-01

The paper presents an analytical method for quantification of low molecular weight (LMW) selenium compounds in human plasma based on liquid chromatography inductively coupled plasma mass spectrometry (LC-ICP-MS) and post column isotope dilution-based quantification. Prior to analysis, samples were ultrafiltrated using a cut-off value of 3000 Da. The method was validated in aqueous solution as well as plasma using standards of selenomethionine (SeMet), Se-methylselenocysteine (MeSeCys), selenite, and the selenosugar Se-methylseleno-N-acetylgalactosamine (SeGal) for linearity, precision, recoveries, and limits of detection and quantitation with satisfactory results. The method was applied for analysis of a set of plasma samples from cancer patients receiving selenite treatment in a clinical trial. Three LMW selenium compounds were observed. The main compounds, SeGal and selenite were tentatively identified by retention time matching with standards in different chromatographic systems, while the third minor compound was not identified. The identity of the selenosugar was verified by ESI-MS-MS product ion scanning, while selenite was identified indirectly as the glutathione (GSH) reaction product, GS-Se-SG.

Application of spectrometric analysis to the identification of pollution sources causing cultural heritage damage.

PubMed

Belfiore, C M; Barca, D; Bonazza, A; Comite, V; La Russa, M F; Pezzino, A; Ruffolo, S A; Sabbioni, C

2013-12-01

Black crusts are recognized to have been, up to now, one of the major deterioration forms affecting the built heritage in urban areas. Their formation is demonstrated to occur mainly on carbonate building materials, whose interaction with an SO2-loaded atmosphere leads to the transformation of calcium carbonate (calcite) into calcium sulfate dihydrate (gypsum) which, together with embedded carbonaceous particles, consequently forms the black crusts on the stone surface. An analytical study was carried out on black crust samples collected from limestone monumental buildings and churches belonging to the European built Heritage, i.e., the Corner Palace in Venice (Italy), the Cathedral of St. Rombouts in Mechelen (Belgium), and the Church of St. Eustache in Paris (France). For a complete characterization of the black crusts, an approach integrating different and complementary techniques was used, including laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), Fourier transform infrared spectroscopy, optical and scanning electron microscopy. In particular, the application of LA-ICP-MS permitted to obtain a complete geochemical characterization in terms of trace elements of the black crusts from the inner parts to the external layers contributing to the identification of the major combustion sources responsible for the deterioration over time of the monuments under study. In addition, the obtained results revealed a relation between the height of sampling and the concentration of heavy metals and proved that the crust composition can be a marker to evaluate the variation of the fuels used over time.

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

EPA Science Inventory

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

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

EPA Science Inventory

Arsenosugars can make up a significant portion of the total arsenic in shellfish. These arsenosugars can be present in their oxide or sulfide form. IC-ICP-MS and IC-ESI-MS/MS data will be presented that indicates the presence of As(328-S) and As(328) in three species of marine ...

ICP-MS/MS-Based Ionomics: A Validated Methodology to Investigate the Biological Variability of the Human Ionome.

PubMed

Konz, Tobias; Migliavacca, Eugenia; Dayon, Loïc; Bowman, Gene; Oikonomidi, Aikaterini; Popp, Julius; Rezzi, Serge

2017-05-05

We here describe the development, validation and application of a quantitative methodology for the simultaneous determination of 29 elements in human serum using state-of-the-art inductively coupled plasma triple quadrupole mass spectrometry (ICP-MS/MS). This new methodology offers high-throughput elemental profiling using simple dilution of minimal quantity of serum samples. We report the outcomes of the validation procedure including limits of detection/quantification, linearity of calibration curves, precision, recovery and measurement uncertainty. ICP-MS/MS-based ionomics was used to analyze human serum of 120 older adults. Following a metabolomic data mining approach, the generated ionome profiles were subjected to principal component analysis revealing gender and age-specific differences. The ionome of female individuals was marked by higher levels of calcium, phosphorus, copper and copper to zinc ratio, while iron concentration was lower with respect to male subjects. Age was associated with lower concentrations of zinc. These findings were complemented with additional readouts to interpret micronutrient status including ceruloplasmin, ferritin and inorganic phosphate. Our data supports a gender-specific compartmentalization of the ionome that may reflect different bone remodelling in female individuals. Our ICP-MS/MS methodology enriches the panel of validated "Omics" approaches to study molecular relationships between the exposome and the ionome in relation with nutrition and health.