Sample records for icp-ms detection limits

  1. 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

  2. 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.

  3. 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.

  4. [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.

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. Analysis and comparison of glass fragments by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and ICP-MS.

    PubMed

    Trejos, Tatiana; Montero, Shirly; Almirall, José R

    2003-08-01

    The discrimination potential of Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) is compared with previously reported solution ICP-MS methods using external calibration (EC) with internal standardization and a newly reported solution isotope dilution (ID) method for the analysis of two different glass populations. A total of 91 different glass samples were used for the comparison study; refractive index and elemental composition were measured by the techniques mentioned above. One set consisted of 45 headlamps taken from a variety of automobiles that represents a range of 20 years of manufacturing dates. A second set consisted of 46 automotive glasses (side windows, rear windows, and windshields) representing casework glass from different vehicle manufacturers over several years. The element menu for the LA-ICP-MS and EC-ICP-MS methods include Mg, Al, Ca, Mn, Ce, Ti, Zr, Sb, Ga, Ba, Rb, Sm, Sr, Hf, La, and Pb. The ID method was limited to the analysis of two isotopes each of Mg, Sr, Zr, Sb, Ba, Sm, Hf, and Pb. Laser ablation analyses were performed with a Q switched Nd:YAG, 266 nm, 6 mJ output energy laser. The laser was used in depth profile mode while sampling using a 50 microm spot size for 50 sec at 10 Hz (500 shots). The typical bias for the analysis of NIST 612 by LA-ICP-MS was less than 5% in all cases and typically better than 5% for most isotopes. The precision for the vast majority of the element menu was determined generally less than 10% for all the methods when NIST 612 was measured (40 microg x g(-1)). Method detection limits (MDL) for the EC and LA-ICP-MS methods were similar and generally reported as less than 1 microg x g(-1) for the analysis of NIST 612. While the solution sample introduction methods using EC and ID presented excellent sensitivity and precision, these methods have the disadvantages of destroying the sample, and also involve complex sample preparation. The laser ablation method was simpler, faster, and

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. Validation of uranium determination in urine by ICP-MS.

    PubMed

    Bouvier-Capely, C; Baglan, N; Montègue, A; Ritt, J; Cossonnet, C

    2003-08-01

    A rapid procedure--dilution of urine+ICP-MS measurement--for the determination of uranium in urine was validated. Large ranges of concentration and isotopic composition were studied on urine samples excreted by occupationally exposed workers. The results were consistent with those obtained by fluorimetry and by alpha spectrometry after a purification procedure, two currently used techniques. However, the proposed procedure is limited for determination of the minor isotope 234U. Thus for worker monitoring, the conversion of 234U mass concentration into activity concentration can lead to an erroneous value of the effective dose, in particular for a contamination at very low level with highly enriched uranium. A solution to avoid this hazard is to perform a chemical purification prior to ICP-MS measurement to lower uncertainty and detection limit for 234U.

  18. 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.

  19. 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).

  20. 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.

  1. 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.

  2. Detection of lead nanoparticles in game meat by single particle ICP-MS following use of lead-containing bullets.

    PubMed

    Kollander, Barbro; Widemo, Fredrik; Ågren, Erik; Larsen, Erik H; Loeschner, Katrin

    2017-03-01

    This study investigated whether game meat may contain nanoparticles of lead from ammunition. Lead nanoparticles in the range 40 to 750 nm were detected by ICP-MS in single particle mode in game shot with lead-containing bullets. The median diameter of the detected nanoparticles was around 60 nm. The particle mass concentration ranged from 290 to 340 ng/g meat and the particle number concentrations from 27 to 50 million particles/g meat. The size limit of detection strongly depended on the level of dissolved lead and was in the range of 40 to 80 nm. In game meat sampled more than 10 cm away from the wound channel, no lead particles with a diameter larger than 40 nm were detected. In addition to dissolved lead in meat that originated from particulates, the presence of lead nano particles in game meat represents a hitherto unattended source of lead with a largely unknown toxicological impact to humans. Graphical Abstract Detection of lead nanoparticles in game meat by single particle ICP-MS following use of leadcontaining bullets.

  3. 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.

  4. Breaking through the uncertainty ceiling in LA-ICP-MS U-Pb geochronology

    NASA Astrophysics Data System (ADS)

    Horstwood, M.

    2016-12-01

    Sources of systematic uncertainty associated with session-to-session bias are the dominant contributor to the 2% (2s) uncertainty ceiling that currently limits the accuracy of LA-ICP-MS U-Pb geochronology. Sources include differential downhole fractionation (LIEF), `matrix effects' and ablation volume differences, which result in irreproducibility of the same reference material across sessions. Current mitigation methods include correcting for LIEF mathematically, using matrix-matched reference materials, annealing material to reduce or eliminate radiation damage effects and tuning for robust plasma conditions. Reducing the depth and volume of ablation can also mitigate these problems and should contribute to the reduction of the uncertainty ceiling. Reducing analysed volume leads to increased detection efficiency, reduced matrix-effects, eliminates LIEF, obviates ablation rate differences and reduces the likelihood of intercepting complex growth zones with depth, thereby apparently improving material homogeneity. High detection efficiencies (% level) and low sampling volumes (20um box, 1-2um deep) can now be achieved using MC-ICP-MS such that low volume ablations should be considered part of the toolbox of methods targeted at improving the reproducibility of LA-ICP-MS U-Pb geochronology. In combination with other strategies these improvements should be feasible on any ICP platform. However, reducing the volume of analysis reduces detected counts and requires a change of analytical approach in order to mitigate this. Appropriate strategies may include the use of high efficiency cell and torch technologies and the optimisation of acquisition protocols and data handling techniques such as condensing signal peaks, using log ratios and total signal integration. The tools required to break the 2% (2s) uncertainty ceiling in LA-ICP-MS U-Pb geochronology are likely now known but require a coherent strategy and change of approach to combine their implementation and realise

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

    PubMed

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

    2015-10-01

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

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. 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.

  12. Advances in HPLC-ICP-MS interface techniques for metal speciation

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

    Hill, S.J.

    The relentless demand for lower detection limits is increasingly coupled to the requirement for elemental speciation. This is particularly true in environmental and clinical fields where total levels are often insufficient for mobility and toxicity studies. This demand for both qualitative and quantitative data on the individual species present in complex samples has led to the development of various interfaces to couple some form of chromatography, usually gas chromatography (GC) or high performance liquid chromatography (HPLC) to an element specific detector. Today inductively coupled plasma-mass spectrometry is often employed since it offers excellent detection limits, element specific information (including isotopicmore » data) and the potential for multi-element studies. Ms presentation will concentrate on HPLC couplings although the advantages and disadvantages of both GC and HPLC couplings to ICP-MS will be discussed. Particular attention will be given to the optimization of both the chromatography and detection systems. Details will be presented of several successful HPLC interface designs and ways of facilitating high levels of a range of organic solvents (e.g. methanol and THF) in the HPLC mobile phase will be highlighted. The advantages of using a sheath gas and practical ways of achieving this will also be discussed. Finally the use of isotope dilution analysis in conjunction with HPLC-ICP-MS will be outlined. In all cases the impact of using the most appropriate approach will be demonstrated using both environmental and clinical samples.« less

  13. 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.

  14. 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.

  15. 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.

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

    USGS Publications Warehouse

    May, T.W.; Wiedmeyer, 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.

  17. Application of isotope-dilution laser ablation ICP-MS for direct determination of Pu concentrations in soils at pg g(-1) levels.

    PubMed

    Boulyga, Sergei F; Tibi, Markus; Heumann, Klaus G

    2004-01-01

    The methods available for determination of environmental contamination by plutonium at ultra-trace levels require labor-consuming sample preparation including matrix removal and plutonium extraction in both nuclear spectroscopy and mass spectrometry. In this work, laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was applied for direct analysis of Pu in soil and sediment samples. Application of a LINA-Spark-Atomizer system (a modified laser ablation system providing high ablation rates) coupled with a sector-field ICP-MS resulted in detection limits as low as 3x10(-13) g g(-1) for Pu isotopes in soil samples containing uranium at a concentration of a few microg g(-1). The isotope dilution (ID) technique was used for quantification, which compensated for matrix effects in LA-ICP-MS. Interferences by UH+ and PbO2+ ions and by the peak tail of 238U+ ions were reduced or separated by use of dry plasma conditions and a mass resolution of 4000, respectively. No other effects affecting measurement accuracy, except sample inhomogeneity, were revealed. Comparison of results obtained for three contaminated soil samples by use of alpha-spectrometry, ICP-MS with sample decomposition, and LA-ICP-IDMS showed, in general, satisfactory agreement of the different methods. The specific activity of (239+240)Pu (9.8 +/- 3.0 mBq g(-1)) calculated from LA-ICP-IDMS analysis of SRM NIST 4357 coincided well with the certified value of 10.4 +/- 0.2 mBq g(-1). However, the precision of LA-ICP-MS for determination of plutonium in inhomogeneous samples, i.e. if "hot" particles are present, is limited. As far as we are aware this paper reports the lowest detection limits and element concentrations yet measured in direct LA-ICP-MS analysis of environmental samples.

  18. 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

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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...

  19. 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.

  20. 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.

  1. 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.

  2. Complementary molecular and elemental detection of speciated thioarsenicals using ESI-MS in combination with a xenon-based collision-cell ICP-MS with application to fortified NIST freeze-dried urine.

    PubMed

    Ellis, Jenny L; Conklin, Sean D; Gallawa, Christina M; Kubachka, Kevin M; Young, Andrea R; Creed, Patricia A; Caruso, Joseph A; Creed, John T

    2008-04-01

    The simultaneous detection of arsenic and sulfur in thioarsenicals was achieved using xenon-based collision-cell inductively coupled plasma (ICP) mass spectrometry (MS) in combination with high-performance liquid chromatography. In an attempt to minimize the (16)O(16)O(+) interference at m/z 32, both sample introduction and collision-cell experimental parameters were optimized. Low flow rates (0.25 mL/min) and a high methanol concentration (8%) in the mobile phase produced a fourfold decrease in the m/z 32 background. A plasma sampling depth change from 3 to 7 mm produced a twofold decrease in background at m/z 32, with a corresponding fourfold increase in the signal associated with a high ionization surrogate for sulfur. The quadrupole bias and the octopole bias were used as a kinetic energy discriminator between background and analyte ions, but a variety of tuning conditions produced similar (less than twofold change) detection limits for sulfur ((32)S). A 34-fold improvement in the (32)S detection limit was achieved using xenon instead of helium as a collision gas. The optimized xenon-based collision cell ICP mass spectrometer was then used with electrospray ionization MS to provide elemental and molecular-based information for the analysis of a fortified sample of NIST freeze-dried urine. The 3sigma detection limits, based on peak height for dimethylthioarsinic acid (DMTA) and trimethylarsine sulfide (TMAS), were 15 and 12 ng/g, respectively. Finally, the peak area reproducibilities (percentage relative standard deviation) of a 5-ppm fortified sample of NIST freeze dried urine for DMTA and TMAS were 7.4 and 5.4%, respectively.

  3. 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.

  4. ICP-MS Workshop

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

    Carman, April J.; Eiden, Gregory C.

    2014-11-01

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

  5. [Effect of the chelator Zn-DTPA on the excretion of lead in lead intoxication mice detected with ICP-MS].

    PubMed

    Li, Chen; Lu, Kai-zhi; Zhou, Qi; Wang, Qiong; Zeng, Yu-liang; Yin, Hong-jun; He, Xuan-hui; Tian, Ying; Dong, Jun-Xing

    2014-11-01

    To study the lead excretion effect of the chelator Zn-DTPA on the lead intoxication mice, inductively coupled plasma mass spectrometry (ICP-MS) was applied to detect the lead content of biological samples. The acute lead intoxication mice model was established by injecting lead acetate intraperitoneally with the dose of 1 mg. Zn-DTPA was administered intraperitoneally to mice once daily for five consecutive days 4 h after intoxication. Control group, model group, combination of Zn-DTPA and Ca-DTPA group were evaluated at the same time. The urine was collected every day. The mice were sacrificed in batches in the 2rd, 4th, 6th day. Biological samples including urine, whole blood, femur and brain were prepared and nitrated. Lead concentration was detected by ICP-MS. The result showed that Zn-DTPA could increase lead content in urine markedly and reduce lead content in blood, femur and brain.

  6. 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.

  7. 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.

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

    PubMed

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

    2017-02-01

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

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

    PubMed Central

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

    2015-01-01

    Laser parameters, typically wavelength, pulse width, irradiance, repetition rate, and pulse energy, are critical parameters which influence the laser ablation process and thereby influence the LA-ICP-MS signal. In recent times, femtosecond laser ablation has gained popularity owing to the reduction in fractionation related issues and improved analytical performance which can provide matrix-independent sampling. The advantage offered by fs-LA is due to shorter pulse duration of the laser as compared to the phonon relaxation time and heat diffusion time. Hence the thermal effects are minimized in fs-LA. Recently, fs-LA-ICP-MS demonstrated improved analytical performance as compared to ns-LA-ICP-MS, but detailed mechanisms and processes are still not clearly understood. Improvement of fs-LA-ICP-MS over ns-LA-ICP-MS elucidates the importance of laser pulse duration and related effects on the ablation process. In this study, we have investigated the influence of laser pulse width (40 fs to 0.3 ns) and energy on LA-ICP-MS signal intensity and repeatability using a brass sample. Experiments were performed in single spot ablation mode as well as rastering ablation mode to monitor the Cu/Zn ratio. The recorded ICP-MS signal was correlated with total particle counts generated during laser ablation as well as particle size distribution. Our results show the importance of pulse width effects in the fs regime that becomes more pronounced when moving from femtosecond to picosecond and nanosecond regimes. PMID:26664120

  10. 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.

  11. 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

    -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.

  12. 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

    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.

  13. 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).

  14. 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).

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

    PubMed

    Hirata, Shizuko; Toshimitsu, Hideki; Aihara, Masato

    2006-01-01

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

  16. Preparation of trout liver microsomes for iron speciation in P-450 enzymes by AE-FPLC with ICP-(ORS)MS detection.

    PubMed

    Rodríguez-Cea, Andrés; de la Campa, María Rosario Fernández; Sanz-Medel, Alfredo

    2005-01-01

    Cytochromes P-450 are members of a superfamily of hemoproteins involved in the oxidative metabolism of various physiological and xenobiotic compounds in eukaryotes and prokaryotes. The multiplicity of this group of enzymes has been widely studied by chromatographic techniques, mainly high-performance liquid chromatography (HPLC). Because these enzymes are membrane-bound proteins, sample preparation for chromatographic separation of P-450 enzymes requires a solubilization step. The sample-preparation procedures are critical, because detergents affect not only the efficiency of protein solubilization but also their further chromatographic resolution. Trout liver microsomes have been taken here as a model sample to investigate iron speciation in cytochrome P-450. Trouts were treated intraperitoneally with beta-naphthoflavone, a potent inducer of some P-450 enzymes, and a microsomal suspension containing 7.4+/-0.1 nmol mL(-1) P-450 enzymes was obtained by ultracentrifugation. Lubrol PX was selected as detergent for solubilization, resulting in about 90% solubilization recovery. The solubilized cytochromes P-450 were further separated by AE-FPLC, with UV detection, or coupled to ICP-MS with an octapole reaction system, ICP-(ORS)MS (monitoring Fe signals at masses 54, 56, and 57). A sampling procedure and chromatographic conditions are developed and were successfully applied to iron speciation in trout liver P-450 enzymes. ICP-(ORS)MS detection of P-450 enzymes is Fe-specific and so will give accurate information on the prosthetic group of the protein, which can constitute an advantageous alternative to classical methods for detection of these hemoproteins.

  17. [Analysis of Arsenic Compounds in Blood and Urine by HPLC-ICP-MS].

    PubMed

    Lin, L; Zhang, S J; Xu, W C; Luo, R X; Ma, D; Shen, M

    2018-02-01

    To establish an analysis method for the detection of 6 arsenic compounds [AsC, AsB, As(Ⅲ), DMA, MMA and As(V)] in blood and urine by high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS), and apply it to real cases. Triton was used to damage cells, and then EDTA·2Na·2H2O was used to complex arsenic compounds in cells, and sonication and protein deposition by acetonitrile were performed for sample pretreatment. With the mobile phase consisted of ammonium carbonate and ultrapure water, gradient elution was performed for obtaining the arsenic compounds in samples, which were analysed by ICP-MS with Hamilton PRP-X100 column. The limits of detection in blood were 1.66-10 ng/mL, while the lower limits of quantitation in blood ranged from 5 to 30 ng/mL. The limits of detection in urine were 0.5-10 ng/mL, while the lower limits of quantitation in urine were 5-30 ng/mL. The relative standard deviation of inter-day and intra-day precisions was less than 10%. This method had been successfully applied to 3 cases. This study has established an analysis method for detecting 6 common arsenic compounds in blood and urine, which can be used to detect the arsenic compounds in the blood and urine from arsenic poisoning cases as well as the patients under arsenic treatment. Copyright© by the Editorial Department of Journal of Forensic Medicine.

  18. 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

  19. 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.

  20. Sequential extractions of selenium soils from Stewart Lake: total selenium and speciation measurements with ICP-MS detection.

    PubMed

    Ponce de León, Claudia A; DeNicola, Katie; Montes Bayón, Maria; Caruso, Joseph A

    2003-06-01

    Different techniques have been employed in order to evaluate the most efficient procedure for the extraction of selenium from soil as required for speciation. Selenium contaminated sediments from Stewart Lake Wetland, California were used. A strong acid mineralization of the samples gives quantitative total selenium, which is then used to estimate recoveries for the milder extraction methods. The different extraction methodologies involve the sequential use of water, buffer (phosphate, pH 7) and either acid solution (e.g. HNO3 or HCl) or basic solutions (e.g. ammonium acetate, NaOH or TMAH). Pyrophosphate extraction was also evaluated and showed that selenium was not associated with humic acids. The extractants were subsequently analyzed by size exclusion chromatography (SEC) with UV (254 and 400 nm) and on-line ICP-MS detection; anion exchange chromatography, and ion-pair reversed phase chromatography with ICP-MS detection. For sequential extractions the extraction efficiencies showed that the basic extractions were more efficient than the acidic. The difference between the acidic and the basic extraction efficiency is carried to the sulfite extraction, suggesting that whatever is not extracted by the acid is subsequently extracted by the sulfite. The species identified with the different chromatographies were selenate, selenite, elemental selenium and some organic selenium.

  1. 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

  2. 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.

  3. Magnetic sulfur-doped porous carbon for preconcentration of trace mercury in environmental water prior to ICP-MS detection.

    PubMed

    Peng, Chuyu; He, Man; Chen, Beibei; Huang, Lijin; Hu, Bin

    2017-11-20

    A novel magnetic sulfur-doped porous carbon (MSPC) was fabricated via a simple one-step carbonization of a mixture of sucrose, basic magnesium sulfate whiskers and Fe 3 O 4 @SiO 2 nanoparticles. Due to the high S content, the prepared MSPC possessed high adsorption capacity for Hg 2+ (343 mg g -1 ) with good selectivity. Based on this, a method coupling magnetic solid phase extraction (MSPE) with inductively coupled plasma mass spectrometry (ICP-MS) was developed for the determination of trace Hg 2+ in environmental water samples. Various parameters such as pH, desorption solvent and its concentration, desorption volume and time, sample volume, and adsorption time that affect the determination have been optimized. Under the optimal conditions, a high enrichment factor of 100-fold was obtained, the limit of detection (LOD) was found to be 0.52 pg mL -1 with a relative standard deviation (c = 10 pg mL -1 , n = 7) of 7.1%, and a good linearity was obtained within the concentration range of 2-5000 pg mL -1 for Hg 2+ . Besides, the proposed method has very fast adsorption/desorption kinetics, target Hg 2+ could be rapidly adsorbed on the prepared MSPC in 2 min and desorbed from the MSPC in 2 min with the assistance of a permanent magnet. Therefore, the proposed method of MSPE-ICP-MS exhibits good application potential in the determination of trace Hg 2+ in environmental water samples.

  4. 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

  5. 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.

  6. Measurement of isotope ratios on transient signals by MC-ICP-MS.

    PubMed

    Günther-Leopold, Ines; Wernli, Beat; Kopajtic, Zlatko; Günther, Detlef

    2004-01-01

    Precise and accurate isotope ratio measurements are an important task in many applications such as isotope-dilution mass spectrometry, bioavailability studies, or the determination of isotope variations in geological or nuclear samples. The technique of MC-ICP-MS has attracted much attention because it permits the precise measurement of isotope compositions for a wide range of elements combined with excellent detection limits due to high ionisation efficiencies. However, the results are based mainly on measurements using continuous sample introduction. In the present study the determination of isotope ratios on various transient signals with a time duration of 30 to 60 s has been achieved by coupling high-performance liquid chromatography to a multicollector inductively coupled plasma mass spectrometer. In order to investigate the origin of ratio drifts across the transient signals for this hyphenated technique, measurements with the same standard solutions were also carried out using a flow-injection device for sample introduction. As a result of this application it could be concluded that the main source of the bias in the measured isotope ratios is within the ICP-MS instead of fractionation effects on the chromatographic column material. Preliminary studies on short transient signals of gaseous samples (dry plasma) showed a reverse fractionation effect compared with wet plasma conditions (flow injection and HPLC).

  7. Analysis of I-Br-Cl in single fluid inclusions by LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Giehl, C.; Fusswinkel, T.; Beermann, O.; Garbe-Schönberg, D.; Scholten, L.; Wagner, T.

    2017-12-01

    Halogens are excellent tracers of hydrothermal fluid sources and in-situ LA-ICP-MS analysis of Cl and Br in single fluid inclusions has provided fundamentally new insight into hydrothermal fluid flow and ore formation. There is mounting evidence that enrichment and depletion of Br relative to Cl may be caused by a number of processes beyond seawater evaporation and halite dissolution which cannot be discriminated on the basis of Br/Cl ratios alone. Expanding the analytical capabilities of fluid inclusion LA-ICP-MS analysis to include iodine would allow to discern between selective and coupled enrichment processes of Cl, Br and I, even in geologically complex samples that are inaccessible to bulk extraction techniques. We present iodine concentration data determined by LA-ICP-MS analysis of synthetic fluid inclusions, using the Sca17 scapolite reference material for external standardization (Seo et al., 2011). Iodine concentrations in Sca17 were determined using the Durango apatite standard. Four starting solutions containing I (0.3, 1.5, 27, 78 µg/g), Br (941, 1403, 2868, 4275 µg/g), Na (30.7, 94.7 mg/g), and Cl (50, 137 mg/g) (analyzed by ICP-OES and ICP-MS at CAU Kiel) were prepared by dissolving reagent grade chemical powders in ultra-pure water. Spherical inclusions (up to 40 µm) were synthesized from the starting solutions in pre-cracked, HF-treated synthetic quartz crystals which were placed in gold capsules and equilibrated at 600°C, 100/200 MPa in cold seal pressure vessels. Fluid inclusion LA-ICP-MS analysis (University of Helsinki) yielded average I concentrations in excellent agreement with the starting solutions (27.3 µg/g ± 14 %RSD for the 27 µg/g solution and 77.6 µg/g ± 8.3 %RSD for the 78 µg/g solution). Average Br and I concentrations deviate less than 10 % from solution concentration values. For the low I concentration solutions, the synthetic inclusions were too small to detect I. Thus, given suitable standard materials and sufficient

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

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

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

    2012-05-01

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

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

    PubMed

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

    2006-02-01

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

  10. 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.

  11. 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...

  12. 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.

  13. 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.

  14. 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.

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

    EPA Science Inventory

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

  16. ICP-MS measurement of natural radioactivity at LNGS

    NASA Astrophysics Data System (ADS)

    Nisi, S.; Copia, L.; Dafinei, I.; di Vacri, M. L.

    2017-10-01

    Rare events search experiments, like those dedicated to the direct evidence of dark matter or neutrinoless double beta decay, are among the most exciting challenges of modern physics. The sensitivity of such experiments is driven by the background, which depends substantially on the radiopurity of the materials used for the experimental apparatus. Cutting edge measurement techniques are needed for a fast, sensitive and efficient screening of these materials and the certification of their production. Trace element measurements of high sensitivity and quick execution are mandatory also in other fields like tracing the geographical origin of food, temporal and geographical assignment of cultural heritage or monitoring environmental radioactivity. This work is an overview of the inorganic mass spectrometry facility available at Gran Sasso National Laboratory (LNGS) for radiopure material screening and is especially focused on its ICP-MS instrumentation. Analytical methods developed to achieve lowest detection limits in different types of matrix, like metals, polymers, crystals and composite materials, are also indicated. Detection limits of 10-18gg-1 for 226Ra, 10-14gg-1 for U and Th and 10-12gg-1 for K are attained through dedicated operation conditions of the instrumentation. Details are given on the results obtained for different experiments ongoing or under construction at LNGS.

  17. 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.

  18. 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.

  19. Recent Developments in MC-ICP-MS for Uranium Isotopic Determination from Small Samples.

    NASA Astrophysics Data System (ADS)

    Field, P.; Lloyd, N. S.

    2016-12-01

    V002: Advances in approaches and instruments for isotope studies Session ID#: 12653 Recent Developments in MC-ICP-MS for Uranium Isotopic Determination from small samples.M. Paul Field 1 & Nicholas S. Lloyd. 1 Elemental Scientific Inc., Omaha, Nebraska, USA. field@icpms.com 2 Thermo Fisher Scientific, Hanna-Kunath-Str. 11, 28199 Bremen, Germany. nicholas.lloyd@thermofisher.com Uranium isotope ratio determination for nuclear, nuclear safeguards and for environmental applications can be challenging due to, 1) the large isotopic differences between samples and 2) low abundance of 234U and 236U. For some applications the total uranium quantities can be limited, or it is desirable to run at lower concentrations for radiological protection. Recent developments in inlet systems and detector technologies allow small samples to be analyzed at higher precisions using MC-ICP-MS. Here we evaluate the combination of Elemental Scientific apex omega desolvation system and microFAST-MC dual loop-loading flow-injection system with the Thermo Scientific NEPTUNE Plus MC-ICP-MS. The inlet systems allow for the automated syringe loading and injecting handling of small sample volumes with efficient desolvation to minimize the hydride interference on 236U. The highest ICP ion sampling efficiency is realized using the Thermo Scientific Jet Interface. Thermo Scientific 1013 ohm amplifier technology allows small ion beams to be measured at higher precision, offering the highest signal/noise ratio with a linear and stable response that covers a wide dynamic range (ca. 1 kcps - 30 Mcps). For nanogram quantities of low enriched and depleted uranium standards the 235U was measured with 1013 ohm amplifier technology. The minor isotopes (234U and 236U) were measured by SEM ion counters with RPQ lens filters, which offer the lowest detection limits. For sample amounts ca. 20 ng the minor isotopes can be moved onto 1013 ohm amplifiers and the 235U onto standard 1011 ohm amplifier. To illustrate the

  20. 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

  1. 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...

  2. [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.

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

    PubMed

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

    2015-02-01

    A new, fast, automated and inexpensive sample pre-treatment method for (99)Tc determination by inductively coupled plasma-mass spectrometry (ICP-MS) detection is presented. The miniaturized approach is based on a lab-on-valve (LOV) system, allowing automatic separation and preconcentration of (99)Tc. Selectivity is provided by the solid phase extraction system used (TEVA resin) which retains selectively pertechnetate ion in diluted nitric acid solution. The proposed system has some advantages such as minimization of sample handling, reduction of reagents volume, improvement of intermediate precision and sample throughput, offering a significant decrease of both time and cost per analysis in comparison to other flow techniques and batch methods. The proposed LOV system has been successfully applied to different samples of environmental interest (water and soil) with satisfactory recoveries, between 94% and 98%. The detection limit (LOD) of the developed method is 0.005 ng. The high durability of the resin and its low amount (32 mg), its good intermediate precision (RSD 3.8%) and repeatability (RSD 2%) and its high extraction frequency (up to 5 h(-1)) makes this method an inexpensive, high precision and fast tool for monitoring (99)Tc in environmental samples. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. [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.

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. 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

  12. 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).

  13. Measurement of plutonium isotope ratios in nuclear fuel samples by HPLC-MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Günther-Leopold, I.; Waldis, J. Kobler; Wernli, B.; Kopajtic, Z.

    2005-04-01

    Radioactive isotopes are traditionally quantified by means of radioactivity counting techniques ([alpha], [beta], [gamma]). However, these methods often require extensive matrix separation and sample purification before the identification of specific isotopes and their relative abundance is possible as it is necessary in the frame of post-irradiation examinations on nuclear fuel samples. The technique of multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is attracting much attention because it permits the precise measurement of the isotope compositions for a wide range of elements combined with excellent limits of detection due to high ionization efficiencies. The present paper describes one of the first applications of an online high-performance liquid chromatographic separation system coupled to a MC-ICP-MS in order to overcome isobaric interferences for the determination of the plutonium isotope composition and concentrations in irradiated nuclear fuels. The described chromatographic separation is sufficient to prevent any isobaric interference between 238Pu present at trace concentrations and 238U present as the main component of the fuel samples. The external reproducibility of the uncorrected plutonium isotope ratios was determined to be between 0.04 and 0.2% (2 s) resulting in a precision in the [per mille sign] range for the isotopic vectors of the irradiated fuel samples.

  14. Determination of 232Th in urine by ICP-MS for individual monitoring purposes.

    PubMed

    Baglan, N; Cossonnet, C; Ritt, J

    2001-07-01

    Thorium is naturally occurring in various ores used for industrial purposes and has numerous applications. This paper sets out to investigate urine analysis as a suitable monitoring approach for workers potentially exposed to thorium. Due to its biokinetic behavior and its low solubility, urinary concentrations are generally very low, requiring therefore high sensitivity analytical methods. An analytical procedure has been developed for detecting 232Th concentrations of below 1 mBq L(-1) quickly and easily. Due to the long half-life (1.41 x 10(10) y) of 232Th, the potential of a procedure based on urine sample dilution and ICP-MS (inductively coupled plasma-mass spectrometry) measurement was investigated first. Two dilution factors were chosen: 100, which is more suitable for long-term measurement trials, and 20, which increases sensitivity. It has been shown that a 100-fold dilution can be used to measure concentrations of below 1 mBq L(-1), whereas a 20-fold one can be used to reach concentrations of below 0.06 mBq L(-1). Then, on the basis of the limitation of the procedure based on urine dilution, the suitable field of application for the different procedures (100-fold and 20-fold dilution and also a chemical purification followed by an ICP-MS measurement) was determined in relation to monitoring objectives.

  15. Multi-element screening by ICP-MS of two specimens of Napoleon's hair.

    PubMed

    Kintz, Pascal; Ginet, Morgane; Cirimele, Vincent

    2006-10-01

    Since 1960, it has been demonstrated by various analytical procedures that high concentrations of arsenic were present in Napoleon's hair. Various authors, indicating that the detected arsenic levels are a consequence of external contamination, have challenged the results of these examinations. In order to shed more light on this historical controversy, we have tested two samples of Napoleon's hair by inductively coupled plasma-mass spectrometry (ICP-MS). The samples of hair were decontaminated with acetone and were cut into small segments. For multi-element screening, hair samples were mineralized in concentrated nitric acid for 1 h at 70 degrees C, diluted 1:40 in specific solution with rhodium as an internal standard, and finally analyzed by ICP-MS on a Thermo Electron ICP/MS X7. Multi-element analysis of Napoleon's hair samples revealed massive amounts of arsenic (42.1 and 37.4 ng/mg), antimony (2.1 and 1.8 ng/mg) and elevated levels of mercury (3.3 and 4.7 ng/mg) and lead (229 and 112 ng/mg). In the case of arsenic, these concentrations, 40 times higher than the normal values, confirm the hypothesis of a significant exposure to arsenic. The concentrations of the other elements, in particular antimony and mercury, are in agreement with the data already known about the therapeutic treatments given to Napoleon, which were based on calomel (salt of mercury) and tartar emetic (antimony).

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

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

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

    2013-08-08

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

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

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

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

    2013-08-08

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

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

    PubMed Central

    Lin, Yunfeng

    2015-01-01

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

  19. 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

  20. 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%).

  1. 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.

  2. 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...

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Profiling of patterned metal layers by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)

    NASA Astrophysics Data System (ADS)

    Bi, Melody; Ruiz, Antonio M.; Gornushkin, Igor; Smith, Ben W.; Winefordner, James D.

    2000-02-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for profiling patterned thin metal layers on a polymer/silicon substrate. The parameters of the laser and ICP-MS operating conditions have been studied and optimized for this purpose. A new laser ablation chamber was designed and built to achieve the best spatial resolution. The results of the profiling by LA-ICP-MS were compared to those obtained from a laser ablation optical emission spectrometry (LA-OES) instrument, which measured the emission of the plasma at the sample surface, and thus, eliminated the time delay caused by the sample transport into the ICP-MS system. Emission spectra gave better spatial resolution than mass spectra. However, LA-ICP-MS provided much better sensitivity and was able to profile thin metal layers (on the order of a few nanometers) on the silicon surface. A lateral spatial resolution of 45 μm was achieved.

  9. 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.

  10. 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.

  11. [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.

  12. 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.

  13. Hyphenation of ultra performance liquid chromatography (UPLC) with inductively coupled plasma mass spectrometry (ICP-MS) for fast analysis of bromine containing preservatives.

    PubMed

    Bendahl, Lars; Hansen, Steen Honoré; Gammelgaard, Bente; Sturup, Stefan; Nielsen, Camilla

    2006-02-24

    Ultra performance liquid chromatography (UPLC) was coupled to inductively coupled plasma mass spectrometry (ICP-MS) for fast analysis of three bromine-containing preservatives, monitoring the 79Br and 81Br isotopes simultaneously. Due to the efficiency of the 1.7 microm column packing material, the resolution of the test substances was only slightly affected when the linear flow velocity was increased from 0.5 to 1.9 mm s(-1). However, the sensitivity of ICP-MS detection decreased when the linear flow velocity was increased from 0.5 to 1.9 mm s(-1). Analytical figures of merit were determined at an intermediate and at a high linear velocity. The precision was better than 2.2% R.S.D. and regression analysis showed that a linear response was achieved at both flow rates (R2 > 0.9993, n = 36). The analysis time was less than 4.5 min at a flow rate of 50 microL min(-1) and limits of detection and quantification were better than 3.3 and 11 microg BrL(-1), respectively. The analysis time was reduced to 2.7 min when the flow rate was increased to 90 microL min(-1) and limits of detection and quantification were better than 20 and 65 microg BrL(-1), respectively. The method was applied for quantitative analysis of bromine-containing preservatives in commercially available cosmetic products.

  14. 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.

  15. 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.

  16. Measurement by ICP-MS of lead in plasma and whole blood of lead workers and controls.

    PubMed Central

    Schütz, A; Bergdahl, I A; Ekholm, A; Skerfving, S

    1996-01-01

    OBJECTIVES: To test a simple procedure for preparing samples for measurement of lead in blood plasma (P-Pb) and whole blood (B-Pb) by inductively coupled plasma mass spectrometry (ICP-MS), to measure P-Pb and B-Pb in lead workers and controls, and to evaluate any differences in the relation between B-Pb and P-Pb between people. METHODS: P-Pb and B-Pb were measured by ICP-MS in 43 male lead smelter workers and seven controls without occupational exposure to lead. For analysis, plasma and whole blood were diluted 1 in 4 and 1 in 9, respectively, with a diluted ammonia solution containing Triton-X 100 and EDTA. The samples were handled under routine laboratory conditions, without clean room facilities. RESULTS: P-Pb was measured with good precision (CV = 5%) even at concentrations present in the controls. Freeze storage of the samples had no effect on the results. The detection limit was 0.015 microgram/l. The P-Pb was 0.15 (range 0.1-0.3) microgram/l in controls and 1.2 (0.3-3.6) micrograms/l in lead workers, although the corresponding B-Pbs were 40 (24-59) micrograms/l and 281 (60-530) micrograms/l (1 microgram Pb/I = 4.8 nmol/l). B-Pb was closely associated with P-Pb (r = 0.90). The association was evidently non-linear; the ratio B-Pb/P-Pb decreased with increasing P-Pb. CONCLUSIONS: By means of ICP-MS and a simple dilution procedure, P-Pb may be measured accurately and with good precision down to concentrations present in controls. Contamination of blood at sampling and analysis is no major problem. With increasing P-Pb, the percentage of lead in plasma increases. In studies of lead toxicity, P-Pb should be considered as a complement to current indicators of lead exposure and risk. PMID:9038796

  17. 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.

  18. 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

    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.

  19. High-precision Ru isotopic measurements by multi-collector ICP-MS.

    PubMed

    Becker, Harry; Dalpe, Claude; Walker, Richard J

    2002-06-01

    Ruthenium isotopic data for a pure Aldrich ruthenium nitrate solution obtained using a Nu Plasma multi collector inductively coupled plasma-mass spectrometer (MC-ICP-MS) shows excellent agreement (better than 1 epsilon unit = 1 part in 10(4)) with data obtained by other techniques for the mass range between 96 and 101 amu. External precisions are at the 0.5-1.7 epsilon level (2sigma). Higher sensitivity for MC ICP-MS compared to negative thermal ionization mass spectrometry (N-TIMS) is offset by the uncertainties introduced by relatively large mass discrimination and instabilities in the plasma source-ion extraction region that affect the long-term reproducibility. Large mass bias correction in ICP mass spectrometry demands particular attention to be paid to the choice of normalizing isotopes. Because of its position in the mass spectrum and the large mass bias correction, obtaining precise and accurate abundance data for 104Ru by MC-ICP-MS remains difficult. Internal and external mass bias correction schemes in this mass range may show similar shortcomings if the isotope of interest does not lie within the mass range covered by the masses used for normalization. Analyses of meteorite samples show that if isobaric interferences from Mo are sufficiently large (Ru/Mo < 10(4)), uncertainties on the Mo interference correction propagate through the mass bias correction and yield inaccurate results for Ru isotopic compositions. Second-order linear corrections may be used to correct for these inaccuracies, but such results are generally less precise than N-TIMS data.

  20. 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.

  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.

  2. 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.

  3. Elemental analysis of silicon based minerals by ultrasonic slurry sampling electrothermal vaporisation ICP-MS.

    PubMed

    Rodríguez, Pablo Fernández; Marchante-Gayón, Juan Manuel; Sanz-Medel, Alfredo

    2006-01-15

    Ultrasonic slurry sampling electrothermal vaporisation inductively coupled plasma mass spectrometry (USS-ETV-ICP-MS) was applied to the elemental analysis of silicate based minerals, such as talc or quartz, without any pre-treatment except the grinding of the sample. The electrothermal vaporisation device consists of a tungsten coil connected to a home-made power supply. The voltage program, carrier gas flow rate and sonication time were optimised in order to obtain the best sensitivity for elements determined. The relationship between the amount of sample in the slurry and the signal intensity was also evaluated. Unfortunately, in all cases, quantification had to be carried out by the standard additions method owing to the strong matrix interferences. The global precision of the proposed method was always better than 12%. The limits of detection, calculated as three times the standard deviation of the blank value divided by the slope of the calibration curve, were between 0.5 ng/g for As and 3.5 ng/g for Ba. The method was validated by comparing the concentrations found for Cu, Mn, Cr, V, Li, Pb, Sn, Mg, U, Ba, Sr, Zn, Sb, Rb and Ce using the proposed methodology with those obtained by conventional nebulisation ICP-MS after acid digestion of the samples in a microwave oven. The concentration range in the solid samples was between 0.2 microg/g for Cr and 60 microg/g for Ba. All results were statistically in agreement with those found by conventional nebulisation.

  4. 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.

  5. Ultrasound assisted enzymatic hydrolysis for isolating titanium dioxide nanoparticles from bivalve mollusk before sp-ICP-MS.

    PubMed

    Taboada-López, María Vanesa; Iglesias-López, Sara; Herbello-Hermelo, Paloma; Bermejo-Barrera, Pilar; Moreda-Piñeiro, Antonio

    2018-08-14

    Applicability of single-particle inductively coupled plasma mass spectrometry (sp-ICP-MS) using dwell times equal to or shorter than 100 μs has been tested for assessing titanium dioxide nanoparticles (TiO 2 NPs) in bivalve mollusks. TiO 2 NPs isolation from fresh mollusk tissues was achieved by ultrasound assisted enzymatic hydrolysis procedure using a pancreatin/lipase mixture. Optimum extraction conditions imply ultrasonication (60% amplitude) for 10 min, and 7.5 mL of a solution containing 3.0 g L -1 of pancreatin and lipase (pH 7.4). The developed method was found to be repeatable (repeatability of 17% for the over-all procedure, TiO 2 NPs concentration of 5.33 × 10 7  ± 8.89 × 10 6 , n = 11), showing a limit of detection of 5.28 × 10 6 NPs g -1 , and a limit of detection in size of 24.4-30.4 nm, based on the 3σ criteria, and on the 3σ/5 σ criteria, respectively. The analytical recovery within the 90-99% range (use of TiO 2 NPs standards of 50 nm at 7 and 14 μg L -1 as Ti). Several bivalve mollusks (clams, cockles, mussels, razor clams, oysters and variegated scallops) were analyzed for total titanium (ICP-MS after microwave assisted acid digestion), and for TiO 2 NPs by the proposed method. TiO 2 NPs concentrations were within the 2.36 × 10 7 -1.25 × 10 8 NPs g -1 range, and the most frequent sizes were from 50 to 70 nm. Copyright © 2018 Elsevier B.V. All rights reserved.

  6. Speciation analysis of inorganic antimony in soil using HPLC-ID-ICP-MS.

    PubMed

    Amereih, Sameer; Meisel, Thomas; Kahr, Elisabeth; Wegscheider, Wolfhard

    2005-12-01

    Speciation analysis of Sb(III) and Sb(V) in a soil sample was performed through extraction and on-line isotope dilution concentration determination after a chromatographic separation. The total Sb concentration found in a through traffic contaminated soil sample was (4.17 microg g(-1), 0.3 microg g(-1) SD, n=6). It was determined using ICP-MS after soil digestion using the sodium peroxide sintering method. The optimized extraction procedure for speciation analysis was carried out using 100 mmol L(-1) citric acid at pH 2.08 by applying an ultrasonic bath for 45 min at room temperature. The effects of citric acid concentration (0-500 mmol L(-1)), pH (1-6), and temperature (30-60 degrees C) on inorganic antimony species distribution in the examined sample were studied and optimized. The separation of Sb(III) and Sb(V) was achieved using an anion exchange column (PRP-X100) and 10 mmol L(-1) EDTA and 1 mmol L(-1) phthalic acid at pH 4.5 as a mobile phase. The eluent from the HPLC was mixed with an enriched (94.2%) (123)Sb spike solution that was pumped by a peristaltic pump with a constant flow rate (0.5 mL min(-1)) in a three-way valve. The blend passed directly to the Conikal nebulizer of the ICP-MS. By using the above extraction procedure and methodology, 43.2% Sb(V) (2.9% RSD, n=3) and 6.0% Sb(III) (1.3% RSD, n=3) of total Sb found in the sample could be detected. The detection limits achieved by the proposed method were 20 ng L(-1) and 65 ng L(-1) for Sb(V) and Sb(III), respectively. The precision, evaluated by using RSD with 100 ng L(-1) calibration solutions, was 2.7% and 3.2% (n=6) for Sb(V) and Sb(III), respectively, in aqueous solutions.

  7. 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.

  8. 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.

  9. Ion-pair chromatography coupled to inductively coupled plasma-mass spectrometry (IPC-ICP-MS) as a method for thiomolybdate speciation in natural waters.

    PubMed

    Lohmayer, Regina; Reithmaier, Gloria Maria Susanne; Bura-Nakić, Elvira; Planer-Friedrich, Britta

    2015-03-17

    Molybdenum precipitates preferentially under reducing conditions; therefore, its occurrence in sediment records is used as an indicator of paleoredox conditions. Although thiomolybdates (MoO4-xSx(2-) with x = 1-4) supposedly are necessary intermediates in the process of molybdenum precipitation under anoxic conditions, there is no information about their abundance in natural environments, because of a lack of element-specific methods with sufficiently low detection limits. Here, we optimized ion-pair chromatographic separation for coupling to an inductively coupled plasma-mass spectrometry detector (IPC-ICP-MS). 2-Propanol (10%-25% gradient) replaced the previously used acetonitrile (25%-75%) as the solvent, to reduce the carbon load into the plasma. In synthetic solutions, formation of thiomolybdates was found to occur spontaneously in the presence of excess sulfide and the degree of thiolation was highest at pH 7. Excess hydroxyl led to a transformation of thiomolybdates to molybdate. Under acidic to neutral conditions, precipitation of molybdenum and hydrolysis of tetrathiomolybdate were observed. Flash-freezing was found to be suitable to stabilize tetrathiomolybdate, with <4% transformation over more than two months. High ionic strengths matrices (>2 mM) negatively affected the detection of molybdate, which eluted mainly in the dead volume, but had no negative effect on higher thiolated molybdates. Detection limits were ∼10 nM. With the newly developed IPC-ICP-MS method, thiomolybdates were found to form spontaneously in euxinic marine waters after adding a molybdate spike and occur naturally in sulfidic geothermal waters.

  10. A New Multielement Method for LA-ICP-MS Data Acquisition from Glacier Ice Cores.

    PubMed

    Spaulding, Nicole E; Sneed, Sharon B; Handley, Michael J; Bohleber, Pascal; Kurbatov, Andrei V; Pearce, Nicholas J; Erhardt, Tobias; Mayewski, Paul A

    2017-11-21

    To answer pressing new research questions about the rate and timing of abrupt climate transitions, a robust system for ultrahigh-resolution sampling of glacier ice is needed. Here, we present a multielement method of LA-ICP-MS analysis wherein an array of chemical elements is simultaneously measured from the same ablation area. Although multielement techniques are commonplace for high-concentration materials, prior to the development of this method, all LA-ICP-MS analyses of glacier ice involved a single element per ablation pass or spot. This new method, developed using the LA-ICP-MS system at the W. M. Keck Laser Ice Facility at the University of Maine Climate Change Institute, has already been used to shed light on our flawed understanding of natural levels of Pb in Earth's atmosphere.

  11. Surface Cleaning Techniques: Ultra-Trace ICP-MS Sample Preparation and Assay of HDPE

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

    Overman, Nicole R.; Hoppe, Eric W.; Addleman, Raymond S.

    2013-06-01

    The world’s most sensitive radiation detection and assay systems depend upon ultra-low background (ULB) materials to reduce unwanted radiological backgrounds. Herein, we evaluate methods to clean HDPE, a material of interest to ULB systems and the means to provide rapid assay of surface and bulk contamination. ULB level material and ultra-trace level detection of actinide elements is difficult to attain, due to the introduction of contamination from sample preparation equipment such as pipette tips, sample vials, forceps, etc. and airborne particulate. To date, literature available on the cleaning of such polymeric materials and equipment for ULB applications and ultra-trace analysesmore » is limited. For these reasons, a study has been performed to identify an effective way to remove surface contamination from polymers in an effort to provide improved instrumental detection limits. Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) was utilized to assess the effectiveness of a variety of leachate solutions for removal of inorganic uranium and thorium surface contamination from polymers, specifically high density polyethylene (HDPE). HDPE leaching procedures were tested to optimize contaminant removal of thorium and uranium. Calibration curves for thorium and uranium ranged from 15 ppq (fg/mL) to 1 ppt (pg/mL). Detection limits were calculated at 6 ppq for uranium and 7 ppq for thorium. Results showed the most effective leaching reagent to be clean 6 M nitric acid for 72 hour exposures. Contamination levels for uranium and thorium found in the leachate solutions were significant for ultralow level radiation detection applications.« less

  12. 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.

  13. Multielement analysis of Zanthoxylum bungeanum Maxim. essential oil using ICP-MS/MS.

    PubMed

    Fu, Liang; Xie, Hualin; Shi, Shuyun

    2018-06-01

    The concentrations of trace elements (Cr, Ni, As, Cd, Hg, and Pb) in Zanthoxylum bungeanum Maxim. essential oil (ZBMEO) were determined by inductively coupled plasma tandem mass spectrometry. The ZBMEO sample was directly analyzed after simple dilution with n-hexane. Aiming for a relatively high vapor pressure of n-hexane and its resultant loading on plasma, we used a narrow injector torch and optimized plasma radio frequency power and carrier gas flow to ensure stable operation of the plasma. An optional gas flow of 20% O 2 in Ar was added to the carrier gas to prevent the incomplete combustion of highly concentrated organic carbon in plasma and the deposition of carbon on the sampling and skimmer cone orifices. In tandem mass spectrometry mode, O 2 was added to the collision/reaction cell to eliminate the interferences. The limits of detection for Cr, Ni, As, Cd, Hg, and Pb were 2.26, 1.64, 2.02, 1.35, 1.76, and 0.97 ng L -1 , respectively. After determination of 23 ZBMEO samples from different regions in China, we found that the average concentration ranges of trace elements in the 23 ZBMEO samples were 0.72-6.02 ng g -1 , 0.09-2.87 ng g -1 , 0.21-5.84 ng g -1 , 0.16-2.15 ng g -1 , 0.13-0.92 ng g -1 , and 0.17-0.73 ng g -1 for Cr, Ni, As, Cd, Hg, and Pb, respectively. The trace elements in ZBMEO differed significantly when different extraction technologies were used. The study revealed that the contents of the toxic elements As, Cd, Hg, and Pb were extremely low, and hence they are unlikely to pose a health risk following ZBMEO ingestion. Graphical abstract The working mechanism of sample analysis by ICP-MS/MS.

  14. 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.

  15. Quantification of 226Ra at environmental relevant levels in natural waters by ICP-MS: Optimization, validation and limitations of an extraction and preconcentration approach.

    PubMed

    Lagacé, François; Foucher, Delphine; Surette, Céline; Clarisse, Olivier

    2017-05-15

    Radium (Ra) at environmental relevant levels in natural waters was determined by ICP-MS after an off-line pre-concentration procedure. The latter consisted of Ra selective elution from potential interfering elements (i.e. other alkaline earth cations: Ba 2+ , Sr 2+ , Ca 2+ , Mg 2+ ) on a series of two different ion exchange resins (AG50W-X8 and Sr-resin). The overall analytical method was optimized according to the instrumental performance, the volume of water sample loaded on resins, and the sample salinity. Longer acquisition time (up to 150 s) was required to ensure stable measurement of Ra by ICP-MS at ultra trace level (1.0pgL -1 ). For a synthetic groundwater spiked with Ra at 10.0pgL -1 , the analytical procedure demonstrated efficient separation of the analyte from its potential interfering elements and a complete recovery, independent of the sample volume tested from 10 up to 100mL. For synthetic seawater spiked at a level of 10.0pgL -1 of Ra, the total load of salts on the two resins should not exceed 0.35g in order to ensure a complete separation and recovery of Ra. The method was validated on natural waters (i.e. groundwater, freshwater and seawater samples) spiked with Ra at different levels (0.0, 0.5, 1.0 and 5.0pgL -1 ). Absolute Ra detection limits were determined at 0.020pgL -1 (0.73mBqL -1 ) and 0.12pgL -1 (4.4mBqL -1 ) respectively for 60.0mL of freshwater sample and for 10.0mL of seawater. Copyright © 2017 Elsevier B.V. All rights reserved.

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

    PubMed

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

    2015-06-01

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

  17. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2006-08-01

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

  19. [Determination of trace Cs, Th and U in ten kinds of human autopsy tissues by ICP-MS].

    PubMed

    Wang, Jing-yu; Zhu, Hong-da; Ouyang, Li; Liu, Ya-qiong; Wang, Xiao-yan; Huang, Zhuo; Wang, Nai-fen; Liu, Hu-sheng

    2004-09-01

    This paper studied the trace elements Cs, Th and U in ten kinds of human autopsy tissues by ICP-MS. The instrumental operating conditions were optimized for the measurement of Cs, Th and U. Rhodium (Rh) was used as an internal standard element to compensate matrix effect. Detection limits for Th, U and Cs were 5.7-17.8 pg x mL(-1). The recoveries for spiking liver samples were 96%-107%, and their RSDs were 4.8%-8.9%. Reference materials of NIST SRM 8414 Bovine and NIST SRM 1486 Bone Meal were analyzed by the described method, and the analytical results agreed well with the reference values. Human autopsy tissues samples were digested by mixed acid (HNO3 + HClO4). The determination of Cs, Th and U in lung, liver, bone, heart, stomach, spleen, muscle, kidney, thyroid gland and intestinum tenue was performed by ICP-MS without separation and enrichment procedures. The obtained results indicated that this method is rapid, sensitive and accurate; the distribution of the three elements is different from one to another human organ sample; the main organ targets for Th and U are lungs and kidneys; and a coordinated variation of Cs, Th and U concentration in lungs was found in the samples collected from Hebei and Sichuan provinces.

  20. 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.

  1. 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.

  2. A comparison of the determination and speciation of inorganic arsenic using general HPLC methodology with UV, MS and MS/MS detection.

    PubMed

    Gilmartin, Gregory; Gingrich, Diane

    2018-04-15

    The determination and speciation of arsenic in natural resources such as drinking water and agricultural soils has been a growing concern in recent years due to its many toxicological effects [1-3]. To speciate and quantitate concentrations of <1 ppm of arsenic, typically an ion chromatograph (IC) interfaced to an inductively coupled plasma mass spectrometer (ICP-MS) is employed [4-9]. This methodology may be very robust and sensitive, but it is expensive and not as ubiquitous as high performance liquid chromatography (HPLC) with ultraviolet (UV) absorbance detection or electrospray ionization mass spectrometry (ESI-MS). Anion exchange chromatography is a well-documented means of speciating arsenite (As(III), As 2 O 3 ) and arsenate (As(V), AsO 4 ) using UV [10], conductivity [11], or ESI-MS detection [12,13]. This paper demonstrates the utilization of common liquid chromatographic instrumentation to speciate and determines inorganic Arsenic compounds using UV or MS via selected ion recording (SIR) or multiple reaction monitoring (MRM) detection. This paper describes the analysis of arsenite and arsenate samples prepared using both deionized and ground water. The limit of quantitation for the techniques described in this paper for samples spiked in ground water were 454 ppb (As(III)) and 562 ppb (As(V)) for UV detection, 45.4 ppb (As(III)) and 56.2 ppb (As(V)) for SIR detection, and 4.54 ppb (As(III)) and 5.62 ppb (As(V)) for MRM detection. Copyright © 2018 Elsevier B.V. All rights reserved.

  3. 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.

  4. 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

  5. 99Tc atom counting by quadrupole ICP-MS. Optimisation of the instrumental response

    NASA Astrophysics Data System (ADS)

    Más, José L.; Garcia-León, Manuel; Bolívar, Juan P.

    2002-05-01

    In this paper, an extensive work is done on the specific tune of a conventional ICP-MS for 99Tc atom counting. For this, two methods have been used and compared: the partial variable control method and the 5D Simplex method. Instrumental limits of detection of 0.2 and 0.8 ppt, respectively, were obtained. They are noticeably lower than that found with the automatic tune method of the spectrometer, 47 ppt, which shows the need of a specific tune when very low levels of 99Tc have to be determined. A study is presented on the mass interferences for 99Tc. Our experiments show that the formation of polyatomic atoms or refractory oxides as well as 98Mo hydrides seem to be irrelevant for 99Tc atom counting. The opposite occurs with the presence of isobaric interferences, i.e. 99Ru, and the effect of abundance sensitivity, or low-mass resolution, which can modify the response at m/ z=99 to a non-negligible extent.

  6. Challenges in the quality assurance of elemental and isotopic analyses in the nuclear domain benefitting from high resolution ICP-OES and sector field ICP-MS.

    PubMed

    Krachler, Michael; Alvarez-Sarandes, Rafael; Van Winckel, Stefaan

    Accurate analytical data reinforces fundamentally the meaningfulness of nuclear fuel performance assessments and nuclear waste characterization. Regularly lacking matrix-matched certified reference materials, quality assurance of elemental and isotopic analysis of nuclear materials remains a challenging endeavour. In this context, this review highlights various dedicated experimental approaches envisaged at the European Commission-Joint Research Centre-Institute for Transuranium Elements to overcome this limitation, mainly focussing on the use of high resolution-inductively coupled plasma-optical emission spectrometry (HR-ICP-OES) and sector field-inductively coupled plasma-mass spectrometry (SF-ICP-MS). However, also α- and γ-spectrometry are included here to help characterise extensively the investigated actinide solutions for their actual concentration, potential impurities and isotopic purity.

  7. 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.

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

    PubMed

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

    2014-08-01

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

  9. 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.

  10. 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

  11. 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

  12. 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 ...

  13. 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.

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

    PubMed

    Karlsson, Stefan; Sjöberg, Viktor; Ogar, Anna

    2015-04-01

    The use of nitrogen as plasma gas for microwave plasma atomic emission spectroscopy (MP AES) is an interesting development in analytical science since the running cost can be significantly reduced in comparison to the inductively coupled argon plasma. Here, we evaluate the performance of the Agilent 4100 MP AES instrument for the analysis of principal metals (Ca, K, Mg, and Na), lithogenic metals (Al, Fe, and Mn) and selected trace metals (As, Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, V, and Zn) in nitric acid plant digests. The digests were prepared by microwave-assisted dissolution of dry plant material from sunflower (Helianthus annuus) in concentrated nitric acid. Comparisons are made with analysis of the same solutions with ICP-MS (Agilent 7500cx) using the octopole reaction system (ORS) in the collision mode for As, Fe, and V. The limits of detection were usually in the low µg L(-1) range and all principal and lithogenic metals were successfully determined with the MP AES and provided almost identical results with the ICP-MS. The same applies for the selected trace metals except for As, Co and Mo where the concentrations were below the detection limit with the MP AES. For successful analysis we recommend that (i) only atom lines are used, (ii) ionization is minimized (e.g. addition of CsNO3) and (iii) the use of internal standards should be considered to resolve spectral interferences. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. 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.

  16. 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.

  17. Total Arsenic, Cadmium, and Lead Determination in Brazilian Rice Samples Using ICP-MS

    PubMed Central

    Buzzo, Márcia Liane; de Arauz, Luciana Juncioni; Carvalho, Maria de Fátima Henriques; Arakaki, Edna Emy Kumagai; Matsuzaki, Richard; Tiglea, Paulo

    2016-01-01

    This study is aimed at investigating a suitable method for rice sample preparation as well as validating and applying the method for monitoring the concentration of total arsenic, cadmium, and lead in rice by using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Various rice sample preparation procedures were evaluated. The analytical method was validated by measuring several parameters including limit of detection (LOD), limit of quantification (LOQ), linearity, relative bias, and repeatability. Regarding the sample preparation, recoveries of spiked samples were within the acceptable range from 89.3 to 98.2% for muffle furnace, 94.2 to 103.3% for heating block, 81.0 to 115.0% for hot plate, and 92.8 to 108.2% for microwave. Validation parameters showed that the method fits for its purpose, being the total arsenic, cadmium, and lead within the Brazilian Legislation limits. The method was applied for analyzing 37 rice samples (including polished, brown, and parboiled), consumed by the Brazilian population. The total arsenic, cadmium, and lead contents were lower than the established legislative values, except for total arsenic in one brown rice sample. This study indicated the need to establish monitoring programs for emphasizing the study on this type of cereal, aiming at promoting the Public Health. PMID:27766178

  18. Monitoring of metallic contaminants in energy drinks using ICP-MS.

    PubMed

    Kilic, Serpil; Cengiz, Mehmet Fatih; Kilic, Murat

    2018-03-09

    In this study, an improved method was validated for the determination of some metallic contaminants (arsenic (As), chromium (Cr), cadmium (Cd), lead (Pb), iron (Fe), nickel (Ni), copper (Cu), Mn, and antimony (Sb)) in energy drinks using inductive coupled plasma mass spectrometry (ICP-MS). The validation procedure was applied for the evaluation of linearity, repeatability, recovery, limit of detection, and quantification. In addition, to verify the trueness of the method, it was participated in an interlaboratory proficiency test for heavy metals in soft drink organized by the LGC (Laboratory of the Government Chemist) Standard. Validated method was used to monitor for the determination of metallic contaminants in commercial energy drink samples. Concentrations of As, Cr, Cd, Pb, Fe, Ni, Cu, Mn, and Sb in the samples were found in the ranges of 0.76-6.73, 13.25-100.96, 0.16-2.11, 9.33-28.96, 334.77-937.12, 35.98-303.97, 23.67-60.48, 5.45-489.93, and 0.01-0.42 μg L -1 , respectively. The results were compared with the provisional guideline or parametric values of the elements for drinking waters set by the WHO (World Health Organization) and EC (European Commission). As, Cd, Cu, and Sb did not exceed the WHO and EC provisional guideline or parametric values. However, the other elements (Cr, Pb, Fe, Ni, and Mn) were found to be higher than their relevant limits at various levels.

  19. Analysis of inorganic and organic constituents of myrrh resin by GC-MS and ICP-MS: An emphasis on medicinal assets.

    PubMed

    Ahamad, Syed Rizwan; Al-Ghadeer, Abdul Rahman; Ali, Raisuddin; Qamar, Wajhul; Aljarboa, Suliman

    2017-07-01

    The aim of the present investigation was to explore the constituents of the Arabian myrrh resin obtained from Commiphora myrrha. The organic and inorganic composition of the myrrh gum resin has been investigated using gas chromatography-mass spectrometry (GC-MS) and inductively coupled plasma-mass spectrometry (ICP-MS). Analysis executed by ICP-MS reveals the presence of various inorganic elements in significant amount in the myrrh resin. The elements that were found to be present in large amounts include calcium, magnesium, aluminum, phosphorus, chlorine, chromium, bromine and scandium. The important organic constituents identified in the myrrh ethanolic extract include limonene, curzerene, germacrene B, isocericenine, myrcenol, beta selinene, and spathulenol,. The present work complements other myrrh associated investigations done in the past and provides additional data for the future researches.

  20. 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.

  1. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2003-09-01

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

  3. Determination and identification of hydrophilic and hydrophobic arsenic species in methanol extract of fresh cod liver by RP-HPLC with simultaneous ICP-MS and ESI-Q-TOF-MS detection.

    PubMed

    Arroyo-Abad, Uriel; Lischka, Susanne; Piechotta, Christian; Mattusch, Jürgen; Reemtsma, Thorsten

    2013-12-01

    The present study was focused on the determination and identification of arsenic species in methanolic extracts of cod liver. Arsenic species were fractionated and the fractions analysed by RP-HPLC-ICP-MS coupled with ESI-Q-TOF-MS. The total concentration of arsenic in the fresh cod liver was analysed by ICP-MS to be 1.53±0.02 mg As kg(-1)w.w. and the extraction recovery was ca. 100% and the column recovery >93%. Besides polar inorganic and methylated arsenic species (>70%) more hydrophobic arsenic-containing fatty acids and hydrocarbons occurred. Based on the mass spectrometric data proposals for molecular structures were elaborated for 20 of the organic As species included 10 arsenic-containing fatty acids (AsFA) and an arsenic-containing hydrocarbon (AsHC) mentioned for the first time in fresh cod liver. Arsenobetaine was found as main water-soluble arsenic compound in cod liver followed by higher molecular mass arsenic-containing fatty acids and hydrocarbons. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

    USGS Publications Warehouse

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

    2012-01-01

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

  5. Determination of 241Am in Urine Using Sector Field Inductively Coupled Plasma Mass Spectrometry (SF-ICP-MS)

    PubMed Central

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

    2016-01-01

    Quantification of 241Am in urine at low levels is important for assessment of individuals’ or populations’ accidental, environmental, or terrorism-related internal contamination, but no convenient, precise method has been established to rapidly determine these low levels. Here we report a new analytical method to measure 241Am as developed and validated at the Centers for Disease Control and Prevention (CDC) by means of the selective retention of Am from urine directly on DGA resin, followed by SF-ICP-MS detection. The method provides rapid results with a Limit of Detection (LOD) of 0.22 pg/L (0.028 Bq/L), which is lower than 1/3 of the C/P CDG for 241Am at 5 days post-exposure. The results obtained by this method closely agree with CDC values as measured by Liquid Scintillation Counting, and with National Institute of Standards Technology (NIST) Certified Reference Materials (CRM) target values. PMID:27375308

  6. Determination of 241Am in Urine Using Sector Field Inductively Coupled Plasma Mass Spectrometry (SF-ICP-MS).

    PubMed

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

    2016-07-01

    Quantification of 241 Am in urine at low levels is important for assessment of individuals' or populations' accidental, environmental, or terrorism-related internal contamination, but no convenient, precise method has been established to rapidly determine these low levels. Here we report a new analytical method to measure 241 Am as developed and validated at the Centers for Disease Control and Prevention (CDC) by means of the selective retention of Am from urine directly on DGA resin, followed by SF-ICP-MS detection. The method provides rapid results with a Limit of Detection (LOD) of 0.22 pg/L (0.028 Bq/L), which is lower than 1/3 of the C/P CDG for 241 Am at 5 days post-exposure. The results obtained by this method closely agree with CDC values as measured by Liquid Scintillation Counting, and with National Institute of Standards Technology (NIST) Certified Reference Materials (CRM) target values.

  7. Determination of the MRI contrast agent Gd-DTPA by SEC-ICP-MS.

    PubMed

    Loreti, Valeria; Bettmer, Jörg

    2004-08-01

    The simultaneous determination of Gd(3+) and Gd-DTPA (DTPA: diethylenetriamino-pentaacetic acid), often used as contrast agent, is described. The proposed approach combines size-exclusion chromatography (SEC) and inductively coupled plasma-mass spectrometry (ICP-MS) for element-selective detection in order to determine also high-molecular Gd-complexes if present. This method was applied to the analysis of urine samples of a patient to whom Gd-DTPA was intravenously administered. The results showed that no conversion or adsorption of Gd-DTPA could be observed in any sample, even free Gd(3+) could not be detected. Urine excretion behaviour was monitored and it was proved that Gd-DTPA was almost completely (>99%) excreted by urination within one day. Traces of Gd-DTPA could be measured in hair samples, but extraction with tetramethylammonium hydroxide (TMAH) resulted in degradation of Gd-DTPA.

  8. Application of ICP-MS as a multi-element detector for sulfur and metal hydride impurities in hydrocarbon matrices.

    PubMed

    Geiger, William M; McSheehy, Shona; Nash, Martin J

    2007-01-01

    Maturation of inductively coupled plasma-mass spectrometry (ICP-MS) in terms of size, reliability, and cost has had a significant impact on its consideration as a viable detector for gas chromatography. Its generally excellent sensitivity for those elements it can measure has been a contributing factor. A method for sulfur speciation in various hydrocarbon products is investigated, as well as sulfur and metal hydride contaminants in high purity hydrocarbon feed stocks. Detection limits for sulfur species in hydrocarbon liquids and gases are approximately 5 and 10 ppb, respectively, as sulfur. Lower detection limits on the order of 100 parts per trillion are achieved for arsine. The use of collision cell technology (CCT) is exploited to remove interferences. CCT has been described elsewhere (1) using helium or helium-hydrogen mixtures for suppression of (16)O(16)O(+) interference with (32)S. In this work, a novel approach is investigated which uses oxygen to remove this interference by shifting it in a comprehensive fashion. The advantage of operating the system at full power with a tandem gas and liquid interface is also discussed.

  9. 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.

  10. Determination of toxic elements in yerba mate by ICP-MS after diluted acid digestion under O2 pressure.

    PubMed

    Pardinho, Renan B; Dalla Vecchia, Paula; Mendes, Ana L G; Bizzi, Cezar A; Mello, Paola A; Duarte, Fabio A; Flores, Erico M M

    2018-10-15

    In this work, a procedure allowing effective digestion of a high mass of yerba mate (up to 1500 mg) using diluted HNO 3, in a system pressurized with oxygen, is proposed. Digests were suitable for direct analysis by ICP-MS, virtually free of interferences. Digestion was performed using 7 mol l -1 HNO 3 and 8 bar O 2 . The digestion efficiency was better than 92% and digests presented a relatively low acidity (<10 mmol HNO 3 ). The limit of quantification was 4.0, 1.0 and 1.0 ng g -1 for As, Cd and Pb, respectively. Under optimized conditions up to 1500 mg of sample were digested and no interferences were observed during analyses by ICP-MS, making this approach suitable for routine determination of As, Cd and Pb in yerba mate and also in agreement with the quality control requirements. Copyright © 2018 Elsevier Ltd. All rights reserved.

  11. 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.

  12. 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

  13. [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.

  14. An environmentally-friendly, highly efficient, gas pressure-assisted sample introduction system for ICP-MS and its application to detection of cadmium and lead in human plasma.

    PubMed

    Cao, Yupin; Deng, Biyang; Yan, Lizhen; Huang, Hongli

    2017-05-15

    An environmentally friendly and highly efficient gas pressure-assisted sample introduction system (GPASIS) was developed for inductively-coupled plasma mass spectrometry. A GPASIS consisting of a gas-pressure control device, a customized nebulizer, and a custom-made spray chamber was fabricated. The advantages of this GPASIS derive from its high nebulization efficiencies, small sample volume requirements, low memory effects, good precision, and zero waste emission. A GPASIS can continuously, and stably, nebulize 10% NaCl solution for more than an hour without clogging. Sensitivity, detection limits, precision, long-term stability, double charge and oxide ion levels, nebulization efficiencies, and matrix effects of the sample introduction system were evaluated. Experimental results indicated that the performance of this GPASIS, was equivalent to, or better than, those obtained by conventional sample introduction systems. This GPASIS was successfully used to determine Cd and Pb by ICP-MS in human plasma. Copyright © 2017 Elsevier B.V. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

    Wildau, Antje; Garbe-Schönberg, Dieter

    2015-04-01

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

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

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

    LaHaye, Nicole L.; Phillips, Mark C.; Duffin, Andrew M.

    2016-01-01

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

  17. 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.

  18. Determination of (236)U and transuranium elements in depleted uranium ammunition by alpha-spectrometry and ICP-MS.

    PubMed

    Desideri, D; Meli, M A; Roselli, C; Testa, C; Boulyga, S F; Becker, J S

    2002-11-01

    It is well known that ammunition containing depleted uranium (DU) was used by NATO during the Balkan conflict. To evaluate the origin of DU (the enrichment of natural uranium or the reprocessing of spent nuclear fuel) it is necessary to directly detect the presence of activation products ((236)U, (239)Pu, (240)Pu, (241)Am, and (237)Np) in the ammunition. In this work the analysis of actinides by alpha-spectrometry was compared with that by inductively coupled plasma mass spectrometry (ICP-MS) after selective separation of ultratraces of transuranium elements from the uranium matrix. (242)Pu and (243)Am were added to calculate the chemical yield. Plutonium was separated from uranium by extraction chromatography, using tri- n-octylamine (TNOA), with a decontamination factor higher than 10(6); after elution plutonium was determined by ICP-MS ((239)Pu and (240)Pu) and alpha-spectrometry ((239+240)Pu) after electroplating. The concentration of Pu in two DU penetrator samples was 7 x 10(-12) g g(-1) and 2 x 10(-11) g g(-1). The (240)Pu/(239)Pu isotope ratio in one penetrator sample (0.12+/-0.04) was significantly lower than the (240)Pu/(239)Pu ratios found in two soil samples from Kosovo (0.35+/-0.10 and 0.27+/-0.07). (241)Am was separated by extraction chromatography, using di(2-ethylhexyl)phosphoric acid (HDEHP), with a decontamination factor as high as 10(7). The concentration of (241)Am in the penetrator samples was 2.7 x 10(-14) g g(-1) and <9.4 x 10(-15) g g(-1). In addition (237)Np was detected at ultratrace levels. In general, ICP-MS and alpha-spectrometry results were in good agreement. The presence of anthropogenic radionuclides ((236)U, (239)Pu,(240)Pu, (241)Am, and (237)Np) in the penetrators indicates that at least part of the uranium originated from the reprocessing of nuclear fuel. Because the concentrations of radionuclides are very low, their radiotoxicological effect is negligible.

  19. Application of SEC-ICP-MS for comparative analyses of metal-containing species in cancerous and healthy human thyroid samples.

    PubMed

    Boulyga, Sergei F; Loreti, Valeria; Bettmer, Jörg; Heumann, Klaus G

    2004-09-01

    Size exclusion chromatography (SEC) was coupled on-line to inductively coupled plasma mass spectrometry (ICP-MS) for speciation study of trace metals in cancerous thyroid tissues in comparison to healthy thyroids aimed to estimation of changes in metalloprotein speciation in pathological tissue. The study showed a presence of species binding Cu, Zn, Cd and Pb in healthy thyroid tissue with a good reproducibility of chromatographic results, whereas the same species could not be detected in cancerous tissues. Thus, remarkable differences with respect to metal-binding species were revealed between healthy and pathological thyroid samples, pointing out a completely different distribution of trace metals in cancerous tissues. The metal-binding species could not be identified in the frame of this work because of a lack of appropriate standards. Nevertheless, the results obtained confirm the suitability of SEC-ICP-MS for monitoring of changes in trace metal distribution in cancerous tissue and will help to better understand the role of metal-containing species in thyroid pathology.

  20. 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.

  1. 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.

  2. 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.

  3. icpTOF: a new way for the detection of synthetic nanoparticles in environmental systems

    NASA Astrophysics Data System (ADS)

    Borovinskaya, Olga; Tanner, Martin; Böhme, Steffi; Gondikas, Andreas

    2016-04-01

    Tons of engineered nanoparticles are yearly released into the environment as a result of human activity and utilization of nano-containing products. Driven by demand and innovations, the production volumes of nanomaterials are predicted to grow further and already in 2020 will reach >500000 tons [1]. The current challenge faced by society is the lack of information about the fate, behavior, and implications of nanomaterials. This gap has to be filled in order to develop an appropriate strategy for the regulation of nanotechnologies. This is not a simple task because we are still unable to detect and monitor nanoparticles once they have been released into the environment. The list of analytical techniques which can be applied for nanoparticle detection in complex media and at environmentally relevant concentrations (ppt-ppb) is very short and for most of the studies complementary approaches are applied. Single particle (sp)-ICP-MS is a new technique which provides an easy and routinely applied way to quantitatively determine size and number concentration of metal-containing nanoparticles [2]. Moreover, element-specific detection makes sp-ICP-MS more tolerant to high levels of natural background (e.g. organic matter, bacteria). The measurement of single particles implies the detection of extremely short signals (100-500 μm) and requires sensitive and fast instrumentation. Sequentially scanning instruments based on quadrupole or sector-field technology cannot accurately measure more than one isotope per particle and determine elemental composition of single particles. A new icpTOF mass spectrometer (TOFWERK AG, Switzerland) provides simultaneous detection over the whole mass range of elements at μs-time resolution and with >3000 mass resolving power. These unique features render the determination of multi-element composition of single nanoparticles possible [3]. This additional information is extremely valuable to study chemical transformations of particles once

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

    PubMed

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

    2016-07-01

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

  5. 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

  6. 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.

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

    USGS Publications Warehouse

    Wolf, Ruth E.; Adams, Monique

    2015-01-01

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

  8. Practical utilization of spICP-MS to study sucrose density gradient centrifugation for the separation of nanoparticles.

    PubMed

    Johnson, Monique E; Montoro Bustos, Antonio R; Winchester, Michael R

    2016-11-01

    Single particle inductively coupled plasma mass spectrometry (spICP-MS) is shown to be a practical technique to study the efficacy of rate-zonal sucrose density gradient centrifugation (SDGC) separations of mixtures of gold nanoparticles (AuNPs) in liquid suspension. spICP-MS enabled measurements of AuNP size distributions and particle number concentrations along the gradient, allowing unambiguous evaluations of the effectiveness of the separation. Importantly, these studies were conducted using AuNP concentrations that are directly relevant to environmental studies (sub ng mL -1 ). At such low concentrations, other techniques [e.g., dynamic light scattering (DLS), transmission and scanning electron microscopies (TEM and SEM), UV-vis spectroscopy, atomic force microscopy (AFM)] do not have adequate sensitivity, highlighting the inherent value of spICP-MS for this and similar applications. In terms of the SDGC separations, a mixture containing three populations of AuNPs, having mean diameters of 30, 80, and 150 nm, was fully separated, while separations of two other mixtures (30, 60, 100 nm; and 20, 50, 100 nm) were less successful. Finally, it is shown that the separation capacity of SDGC can be overwhelmed when particle number concentrations are excessive, an especially relevant finding in view of common methodologies taken in nanotechnology research. Graphical Abstract Characterization of the separation of a gold nanoparticle mixture by sucrose density gradient centrifugation by conventional and single particle ICP-MS analysis.

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. Fate of nanoparticles during alum and ferric coagulation monitored using single particle ICP-MS.

    PubMed

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

    2018-03-01

    In this study, aluminum sulfate, ferric sulfate, ferric chloride, and poly(diallyldimethylammonium chloride) (pDADMAC) coagulation removal of citrate-stabilized silver and gold nanoparticles (NPs) and uncoated titanium dioxide, cerium dioxide, and zinc oxide NPs was investigated using a single particle (SP) ICP-MS direct monitoring technique. Zone 2 (charge neutralization) coagulation was performed in river water and more commonly used Zone 4 (sweep floc) coagulation was performed in both river and lake water with environmentally relevant concentrations of selected NPs added. SP-ICP-MS was used to detect NP and dissolved species, characterize the size distribution, and quantify particle concentration as well as dissolved species before and after treatments. Other parameters including pH, dissolved organic carbon, turbidity, and UV 254 absorbance were monitored to characterize treatment efficiency. Charge neutralization (Zone 2) coagulation resulted in 48-85% removal of citrate-stabilized NPs and 90-99% removal of uncoated NPs from river water. Sweep floc (Zone 4) coagulation in river water resulted in 36-94% removal of citrate-stabilized NPs and 91-99% removal of uncoated NPs both with and without polymer addition. Zone 4 coagulation conditions in lake water resulted in 77-98% removal of citrate-stabilized NPs and 59-96% removal of uncoated NPs without polymer. These results indicate that NP removal depends on NP surface and stability, the nature of the source water, and the coagulant type and approach. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. 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.

  15. 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

  16. Determination of Plutonium Isotope Ratios at Very Low Levels by ICP-MS using On-Line Electrochemically Modulated Separations

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

    Liezers, Martin; Lehn, Scott A; Olsen, Khris B

    2009-10-01

    Electrochemically modulated separations (EMS) are shown to be a rapid and selective means of extracting and concentrating Pu from complex solutions prior to isotopic analysis by inductively coupled plasma mass spectrometry (ICP-MS). This separation is performed in a flow injection mode, on-line with the ICP-MS. A three-electrode, flow-by electrochemical cell is used to accumulate Pu at an anodized glassy carbon electrode by redox conversion of Pu(III) to Pu (IV&VI). The entire process takes place in 2% v/v (0.46M) HNO 3. No redox chemicals or acid concentration changes are required. Plutonium accumulation and release is redox dependent and controlled by themore » applied cell potential. Thus large transient volumetric concentration enhancements can be achieved. Based on more negative U(IV) potentials relative to Pu(IV), separation of Pu from uranium is efficient, thereby eliminating uranium hydride interferences. EMS-ICP-MS isotope ratio measurement performance will be presented for femtogram to attogram level plutonium concentrations.« less

  17. 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.

  18. 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.

  19. 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.

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

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

    Gallimore, David L.

    2012-06-13

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

  1. 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.

  2. 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.

  3. Chromium(III)-imprinted silica gel for speciation analysis of chromium in environmental water samples with ICP-MS detection.

    PubMed

    Zhang, Nan; Suleiman, Jibrin Sabo; He, Man; Hu, Bin

    2008-04-15

    A new chromium(III)-imprinted 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTS)-functionalized silica gel sorbent was synthesized by a surface imprinting technique and was employed as a selective solid-phase extraction material for speciation analysis of chromium in environmental water samples prior to its determination by inductively coupled plasma mass spectrometry (ICP-MS). The prepared Cr(III)-imprinted silica gel shows the selectivity coefficient of more than 700 for Cr(III) in the presence of Mn(II). The static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Cr(III) were 30.5 mg g(-1) and 13.4 mg g(-1). It was also found that Cr(VI) could be adsorbed at low pH by the prepared imprinted silica gel, and this finding makes it feasible to enrich and determine Cr(VI) at low pH without adding reducing reagents. The imprinted silica gel sorbent offered a fast kinetics for the adsorption and desorption of both chromium species. Under the optimized conditions, the detection limits of 4.43 pg mL(-1) and 8.30 pg mL(-1) with the relative standard deviations (R.S.D.s) of 4.44% and 4.41% (C=0.5 ng mL(-1), n=7) for Cr(III) and Cr(VI) were obtained, respectively. The proposed method was successfully applied to the speciation of trace chromium in environmental water samples. To validate the proposed method, two certified reference materials were analyzed and the determined values were in a good agreement with the certified values. The developed method is rapid, selective, sensitive and applicable for the speciation of trace chromium in environmental water samples.

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

    PubMed

    Ozen, Sukran Akkus; Yaman, Mehmet

    2016-08-02

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

  5. 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.

  6. 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

  7. LC-ICP-MS analysis of arsenic compounds in dominant seaweeds from the Thermaikos Gulf (Northern Aegean Sea, Greece).

    PubMed

    Pell, Albert; Kokkinis, Giannis; Malea, Paraskevi; Pergantis, Spiros A; Rubio, Roser; López-Sánchez, José Fermín

    2013-11-01

    The content of total arsenic and arsenic compounds in the dominant seaweed species in the Thermaikos Gulf, Northern Aegean Sea was determined in samples collected in different seasons. Total arsenic was determined by acid digestion followed by ICP-MS. Arsenic speciation was analyzed by water extraction followed by LC-ICP-MS. Total arsenic concentrations in the seaweeds ranged from 1.39 to 55.0 mg kg(-1). Cystoseira species and Codium fragile showed the highest total As contents, while Ulva species (U. intestinalis, U. rigida,U. fasciata) had the lowest Arsenosugars, the most common arsenic species in seaweeds, were found in all samples, and glycerol-arsenosugar was the most common form; however, phosphate-arsenosugar and sulfate-arsenosugar were also present. Inorganic arsenic was measured in seven algae species and detected in another. Arsenate was the most abundant species in Cystoseira barbata (27.0 mg kg(-1)). Arsenobetaine was measured in only one sample. Methylated arsenic species were measured at very low concentrations. The information should contribute to further understanding the presence of arsenic compounds in dominant seaweeds from the Thermaikos Gulf. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. 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.

  9. 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

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. Resolution of rare earth element interferences in fossil energy by-product samples using sector-field ICP-MS

    DOE PAGES

    Thompson, Robert L.; Bank, Tracy; Roth, Elliot; ...

    2016-07-30

    Here, the supply and price of rare earth elements (REEs) have become a concern to many countries in the world, which has led to renewed interest in exploration and recovery of REEs from secondary or waste sources. Potential high REE waste sources that are of particular interest are coal mining, preparation, combustion, and other fossil energy by-products, including those from natural gas production. In this work, we have examined a set of five solid samples from the treatment of produced and flowback water containing elevated concentrations of barium. In order to confirm the correct concentrations of Eu, we studied thesemore » materials using sector field inductively coupled plasma mass spectrometry (SF-ICP-MS), which is capable of resolving species of nearly identical masses, including Eu and BaO. While the use of quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) for the REE analysis of most geological sample matrices should pose no problem, the presence of large amounts of Ba, as encountered in water treatment solids from natural gas produced and flowback samples may require SF-ICP-MS for accurate determination of all REEs.« less

  16. 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

  17. A Novel Detection Platform for Shrimp White Spot Syndrome Virus Using an ICP11-Dependent Immunomagnetic Reduction (IMR) Assay.

    PubMed

    Liu, Bing-Hsien; Lin, Yu-Chen; Ho, Chia-Shin; Yang, Che-Chuan; Chang, Yun-Tsui; Chang, Jui-Feng; Li, Chun-Yuan; Cheng, Cheng-Shun; Huang, Jiun-Yan; Lee, Yen-Fu; Hsu, Ming-Hung; Lin, Feng-Chun; Wang, Hao-Ching; Lo, Chu-Fang; Yang, Shieh-Yueh; Wang, Han-Ching

    2015-01-01

    Shrimp white spot disease (WSD), which is caused by white spot syndrome virus (WSSV), is one of the world's most serious shrimp diseases. Our objective in this study was to use an immunomagnetic reduction (IMR) assay to develop a highly sensitive, automatic WSSV detection platform targeted against ICP11 (the most highly expressed WSSV protein). After characterizing the magnetic reagents (Fe3O4 magnetic nanoparticles coated with anti ICP11), the detection limit for ICP11 protein using IMR was approximately 2 x 10(-3) ng/ml, and the linear dynamic range of the assay was 0.1~1 x 10(6) ng/ml. In assays of ICP11 protein in pleopod protein lysates from healthy and WSSV-infected shrimp, IMR signals were successfully detected from shrimp with low WSSV genome copy numbers. We concluded that this IMR assay targeting ICP11 has potential for detecting the WSSV.

  18. Lanthanides determination in red wine using ultrasound assisted extraction, flow injection, aerosol desolvation and ICP-MS.

    PubMed

    Bentlin, Fabrina R S; dos Santos, Clarissa M M; Flores, Erico M M; Pozebon, Dirce

    2012-01-13

    This paper deals with the determination of the fourteen naturally occurring elements of the lanthanide series in red wine. Ultrasound (US) was used for sample preparation prior lanthanides determination using ICP-MS. Flow injection (FI) and pneumatic nebulization/aerosol desolvation were used for nebulization of aliquots of 50 μL of sample and its subsequent transportation to plasma. Sample preparation procedures, matrix interference and time of sonication were evaluated. Better results for lanthanides in red wine were obtained by sonication with US probe for 90 s and sample 10-fold diluted. The limits of detection of La, Ce, Nd, Sm, Gd, Pr, Eu, Tb, Dy, Ho, Er, Tm, Lu and Yb were 6.57, 10.8, 9.97, 9.38, 2.71, 1.29, 1.22, 0.52, 2.35, 0.96, 2.30, 0.45, 0.24 and 1.35 ng L(-1), respectively. Red wines of different varieties from three countries of South America were discriminated according to the country of origin by means of multivariate analysis of lanthanides concentration. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. 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.

  20. Direct determination of lead in biological samples by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) after furnace-fusion in the sample cuvette-tungsten boat furnace.

    PubMed

    Okamoto, Y

    2000-06-01

    The newly conceived electrothermal vaporization (ETV) system using a tungsten boat furnace (TBF) sample cuvette was designed for the direct analysis of solid samples with detection by inductively coupled plasma mass spectrometry (ICP-MS). Into this small sample cuvette, a solid mixture of the biological samples and diammonium hydrogenphosphate powder as a fusion flux was placed and situated on a TBF. Tetramethylammonium hydroxide solution was added to the mixture. After the on-furnace digestion had been completed, the analyte in the cuvette was vaporized and introduced into the ICP mass spectrometer. The solid samples were analyzed by using a calibration curve prepared from the aqueous standard solutions. The detection limit was estimated to be 5.1 pg of lead, which corresponds to 10.2 ng g(-1) of lead in solid samples when a prepared sample amount of 1.0 mg was applied. The relative standard deviation for 8 replicate measurements obtained with 100 pg of lead was calculated to be 6.5%. The analytical results for various biological samples are described.

  1. Practical and quality-control aspects of multi-element analysis with quadrupole ICP-MS with special attention to urine and whole blood.

    PubMed

    De Boer, Jan L M; Ritsema, Rob; Piso, Sjoerd; Van Staden, Hans; Van Den Beld, Wilbert

    2004-07-01

    Two screening methods were developed for rapid analysis of a great number of urine and blood samples within the framework of an exposure check of the population after a firework explosion. A total of 56 elements was measured including major elements. Sample preparation consisted of simple dilution. Extensive quality controls were applied including element addition and the use of certified reference materials. Relevant results at levels similar to those found in the literature were obtained for Co, Ni, Cu, Zn, Sr, Cd, Sn, Sb, Ba, Tl, and Pb in urine and for the same elements except Ni, Sn, Sb, and Ba in blood. However, quadrupole ICP-MS has limitations, mainly related to spectral interferences, for the analysis of urine and blood, and these cause higher detection limits. The general aspects discussed in the paper give it wider applicability than just for analysis of blood and urine-it can for example be used in environmental analysis.

  2. Trace Element Determination and Cardioprotection of Terminalia pallida Fruit Ethanolic Extract in Isoproterenol Induced Myocardial Infarcted Rats by ICP-MS.

    PubMed

    Althaf Hussain, Shaik; Kareem, Mohammed Abdul; Rasool, Shaik Nayab; Al Omar, Suliman Yousef; Saleh, Alwasel; Al-Fwuaires, Manal Abdulrahman; Daddam, Jayasimha Rayalu; Devi, Kodidhela Lakshmi

    2018-01-01

    The trace elements and minerals in Terminalia pallida fruit ethanolic extract (TpFE) were determined by the instrument inductively coupled plasma-mass spectrometry (ICP-MS), and the cardioprotection of TpFE against isoproterenol (ISO)-administered rats was studied. Rats were pretreated with TpFE (100, 300, and 500 mg/kg bw) for 30 days, with concurrent administration of ISO (85 mg/kg bw) for two consecutive days. The levels of trace elements and minerals in TpFE were below the permitted limits of World Health Organization standards. ISO administration significantly increased the heart weight and cardiac marker enzymes in serum, xanthine oxidase, sodium, and calcium in the heart, whereas significantly decreased body weight, reduced glutathione, glutathione-S-transferase, superoxide dismutase, and potassium in the heart. Oral pretreatment of TpFE significantly prevented the ISO-induced alterations. This is the first report that revealed the determination of trace elements and mineral nutrients of TpFE by ICP-MS which plays a principal role in the herbal drug discovery for the treatment of cardiovascular diseases.

  3. 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.

  4. 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.

  5. Novel separation method for highly sensitive speciation of cancerostatic platinum compounds by HPLC-ICP-MS.

    PubMed

    Hann, S; Stefánka, Zs; Lenz, K; Stingeder, G

    2005-01-01

    A high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) method is presented for analysis of cisplatin, monoaquacisplatin, diaquacisplatin, carboplatin, and oxaliplatin in biological and environmental samples. Chromatographic separation was achieved on pentafluorophenylpropyl-functionalized silica gel. For cisplatin, carboplatin, and oxaliplatin limits of detection of 0.09, 0.10, and 0.15 microg L(-1), respectively, were calculated at m/z 194, using aqueous standard solutions. (3 microL injection volume). The method was utilized for model experiments studying the stability of carboplatin and oxaliplatin at different chloride concentrations simulating wastewater and surface water conditions. It was found that a high fraction of carboplatin is stable in ultrapure water and in solutions containing 1.5 mol L(-1) Cl-, whereas oxaliplatin degradation was increased by increasing the chloride concentration. In order to support the assessment of oxaliplatin eco-toxicology, the method was tested for speciation of patient urine. The urine sample contained more than 17 different reaction products, which demonstrates the extensive biotransformation of the compound. In a second step of the study the method was successfully evaluated for monitoring cancerostatic platinum compounds in hospital waste water.

  6. [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.

  7. Development of an electrothermal vaporization ICP-MS method and assessment of its applicability to studies of the homogeneity of reference materials.

    PubMed

    Friese, K C; Grobecker, K H; Wätjen, U

    2001-07-01

    A method has been developed for measurement of the homogeneity of analyte distribution in powdered materials by use of electrothermal vaporization with inductively coupled plasma mass spectrometric (ETV-ICP-MS) detection. The method enabled the simultaneous determination of As, Cd, Cu, Fe, Mn, Pb, and Zn in milligram amounts of samples of biological origin. The optimized conditions comprised a high plasma power of 1,500 W, reduced aerosol transport flow, and heating ramps below 300 degrees C s(-1). A temperature ramp to 550 degrees C ensured effective pyrolysis of approximately 70% of the organic compounds without losses of analyte. An additional hold stage at 700 degrees C led to separation of most of the analyte signals from the evaporation of carbonaceous matrix compounds. The effect of time resolution of signal acquisition on the precision of the ETV measurements was investigated. An increase in the number of masses monitored up to 20 is possible with not more than 1% additional relative standard deviation of results caused by limited temporal resolution of the transient signals. Recording of signals from the nebulization of aqueous standards in each sample run enabled correction for drift of the sensitivity of the ETV-ICP-MS instrument. The applicability of the developed method to homogeneity studies was assessed by use of four certified reference materials. According to the best repeatability observed in these sample runs, the maximum contribution of the method to the standard deviation is approximately 5% to 6% for all the elements investigated.

  8. 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.

  9. Multianalytical determination of trace elements in atmospheric biomonitors by k0-INAA, ICP-MS and AAS

    NASA Astrophysics Data System (ADS)

    Freitas, M. C.; Pacheco, A. M. G.; Dionísio, I.; Sarmento, S.; Baptista, M. S.; Vasconcelos, M. T. S. D.; Cabral, J. P.

    2006-08-01

    Elemental contents of atmospheric biomonitors—epiphytic lichens and tree bark, exposed in continuous and discontinuous modes—have been assessed through k0-standardised instrumental neutron activation analysis ( k0-INAA) (two different institutions), inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS). Certified reference materials—ISE-921 (river clay), NIST-1547 (peach leaves), ICHTJ-INCT-TL-1 (tea leaves; TL-1 hereinafter) and IAEA-336 (lichen material), and nonparametric statistics—rank-order correlations (Spearman RS) and enhanced-sign tests (Wilcoxon T)—were used for analytical control and data comparison, respectively. In general, quality of procedures was deemed good, except for k0-INAA in determining Br, Cu and Na, all likely affected by high counting statistics, and/or contamination issues (the latter). Results for Cu, Ni, Pb and Sr (by both ICP-MS and AAS) revealed that, despite an outstanding correlation (asymptotic p=0.000), they could be viewed as statistically equal for Cu only: AAS tended to yield higher values for Pb and Ni, and lower ones for Sr. The comparison between ICP-MS and k0-INAA data from TUDelft, for Al, Ca, Cu, Mg, Mn, Na, Ti and V, showed an excellent correlation (as above) and random (relative) magnitude for Cu, Mg, Mn and Ti only: ICP-MS tended to yield higher values for Al, Na and V, and lower ones for Ca, whereas between k0-INAA data from TUDelft and ITN, for Br, Ca and Na, resulted in systematically higher [Br] and [Ca] variates from TUDelft, even if all corresponding data sets were found to correlate at stringent significance levels. In a few cases, though—Ca, Sr in lichens; Pb in bark—matrix effects did appear to interfere in the outcome of matched-pairs, signed-rank tests, since random hierarchy of variates could be asserted just when lichen and bark data sets were processed separately.

  10. 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.

  11. 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

  12. 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

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

    PubMed Central

    2010-01-01

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

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. Fast and Simple Analytical Method for Direct Determination of Total Chlorine Content in Polyglycerol by ICP-MS.

    PubMed

    Jakóbik-Kolon, Agata; Milewski, Andrzej; Dydo, Piotr; Witczak, Magdalena; Bok-Badura, Joanna

    2018-02-23

    The fast and simple method for total chlorine determination in polyglycerols using low resolution inductively coupled plasma mass spectrometry (ICP-MS) without the need for additional equipment and time-consuming sample decomposition was evaluated. Linear calibration curve for 35 Cl isotope in the concentration range 20-800 µg/L was observed. Limits of detection and quantification equaled to 15 µg/L and 44 µg/L, respectively. This corresponds to possibility of detection 3 µg/g and determination 9 µg/g of chlorine in polyglycerol using studied conditions (0.5% matrix-polyglycerol samples diluted or dissolved with water to an overall concentration of 0.5%). Matrix effects as well as the effect of chlorine origin have been evaluated. The presence of 0.5% (m/m) of matrix species similar to polyglycerol (polyethylene glycol-PEG) did not influence the chlorine determination for PEGs with average molecular weights (MW) up to 2000 Da. Good precision and accuracy of the chlorine content determination was achieved regardless on its origin (inorganic/organic). High analyte recovery level and low relative standard deviation values were observed for real polyglycerol samples spiked with chloride. Additionally, the Combustion Ion Chromatography System was used as a reference method. The results confirmed high accuracy and precision of the tested method.

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

    NASA Astrophysics Data System (ADS)

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

    2011-01-01

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

  1. 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.

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

    PubMed Central

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

    2016-01-01

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

  3. ICP-MS measurement of silver diffusion coefficient in graphite IG-110 between 1048K and 1284K

    NASA Astrophysics Data System (ADS)

    Carter, L. M.; Seelig, J. D.; Brockman, J. D.; Robertson, J. D.; Loyalka, S. K.

    2018-01-01

    Silver-110m has been shown to permeate intact silicon carbide and pyrolytic carbon coating layers of the TRISO fuel particles during normal High Temperature Gas-Cooled Reactor (HTGR) operational conditions. The diffusion coefficients for silver in graphite IG-110 measured using a release method designed to simulate HTGR conditions of high temperature and flowing helium in the temperature range 1048-1253 K are reported. The measurements were made using spheres milled from IG-110 graphite that were infused with silver using a pressure vessel technique. The Ag diffusion was measured using a time release technique with an ICP-MS instrument for detection. The results of this work are:

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Biocompatible Polymer Nanoformulation To Improve the Release and Safety of a Drug Mimic Molecule Detectable via ICP-MS.

    PubMed

    Ferrari, Raffaele; Talamini, Laura; Violatto, Martina Bruna; Giangregorio, Paola; Sponchioni, Mattia; Morbidelli, Massimo; Salmona, Mario; Bigini, Paolo; Moscatelli, Davide

    2017-01-03

    Fluorescent poly(ε-caprolactone)-based nanoparticles (NPs) have been synthesized and successfully loaded with a titanium organometallic compound as a mimic of a water-insoluble drug. The nature of this nanovector enabled us to combine the quantification of the metal in tissues after systemic administration in healthy immunocompetent mice by inductively coupled plasma mass spectroscopy (ICP-MS) followed by the visualization of NPs in organ sections by confocal microscopy. This innovative method of nanodrug screening has enabled us to elucidate the crucial parameters of their kinetics. The organometallic compound is a good mimic of most anticancer drugs, and this approach is an interesting starting point to design the relevance of a broad range of nanoformulations in terms of safety and targeted delivery of the cargoes.

  10. 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

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

    PubMed

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

    2016-05-15

    Tea is one of the most common and popular beverages spanning vast array of cultures all over the world. The main nutritional benefits of drinking tea are its anti-oxidant properties, presumed protection against certain cancers, inhibition of inflammation and possible protective effects against diabetes. Laser induced breakdown spectrometer (LIBS) was assembled as a powerful tool for qualitative and quantitative analysis of various brands of tea samples using 266 nm pulsed UV laser. LIBS spectra for six brands of tea samples in the wavelength range of 200-900 nm was recorded and all elements present in our tea samples were identified. The major toxic elements detected in several brands of tea samples were bromine, chromium and minerals like iron, calcium, potassium and silicon. The spectral assignment was conducted prior to the determination of concentration of each element. For quantitative analysis, calibration curves were drawn for each element using standard samples prepared in known concentration in the tea matrix. The plasma parameters (electron temperature and electron density) were also determined prior to the tea samples spectroscopic analysis. The concentration of iron, chromium, potassium, bromine, copper, silicon and calcium detected in all tea samples was between 378-656, 96-124, 1421-6785, 99-1476, 17-36, 2-11 and 92-130 mg L(-1) respectively. The limits of detection estimated for Fe, Cr, K, Br, Cu, Si, Ca in tea samples were 22, 12, 14, 11, 6, 1 and 12 mg L(-1) respectively. To further confirm the accuracy of our LIBS results, we determined the concentration of each element present in tea samples by using standard analytical technique like ICP-MS. The concentrations detected with our LIBS system are in excellent agreement with ICP-MS results. The system assembled for spectral analysis in this work could be highly applicable for testing the quality and purity of food and also pharmaceuticals products. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. 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.

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

    PubMed

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

    2014-09-01

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

  14. Gunshot residue (GSR) analysis by single particle inductively coupled plasma mass spectrometry (spICP-MS).

    PubMed

    Heringer, Rodrigo D; Ranville, James F

    2018-05-25

    Single particle inductively coupled plasma mass spectrometry (spICP-MS) was investigated as a screening-level technique for the analysis and characterization of inorganic gunshot residue (IGSR) nanoparticles. spICP-MS works with undigested samples whereby nanoparticles (NPs) in a suspension are individually atomized and ionized as they reach the plasma, each resulting in a pulse of analyte ions that can be quantified. The method is rapid, and signals from hundreds of NPs can be collected in 1-2min per sample. The technique is quantitative for NP mass and number concentration when only one element (single element mode) is measured using a quadrupole MS. Likewise, a qualitative elemental fingerprint can be obtained for individual NPs when peak-hopping between two elements (dual element mode). For this proof of concept study, each shooter's hand was sampled with ultrapure water or swab to obtain NPs suspensions. Measurements of antimony, barium, and lead were performed using both analysis modes. With no sample preparation and fully automated sample introduction, it is possible to analyze more than 100 samples in a day. Results show that this technique opens a new perspective for future research on GSR sample identification and characterization and can complement SEM/EDX analysis. Copyright © 2018 Elsevier B.V. All rights reserved.

  15. Analysis of molybdenum, tungsten, and vanadium in surface water of the Atlantic Ocean using solid phase extraction with 8-hydroxyquinoline and ICP MS determination

    NASA Astrophysics Data System (ADS)

    Rimskaya-Korsakova, M. N.; Berezhnaya, E. D.; Dubinin, A. V.

    2017-07-01

    An analytical technique is proposed to determine ultratrace concentrations of Mo, V, and W found in seawater using mass spectrometry with inductively coupled plasma (ICP MS) after preliminary concentration by solid-phase extraction of metal complexes with 8-hydroxyquinoline (8-HQ) on C18 octadecyl silica. The technique utilizes 150 mL of a water sample. A preconcentration factor 50 is obtained. The detection limits are 0.25 nmol/kg, 0.041 nmol/kg, and 5 pmol/kg for Mo, V, and W, respectively. Dissolved Mo, V, and Wconcentrations in surface seawater from Atlantic Ocean transect were determined. The concentrations ranges along the transect were: 91-108 nmol/kg for Mo, 28-35 nmol/kg for V, and 55-75 pmol/kg for W. The Mo/W ratio varied from 1300 to 1800.

  16. Investigation of Trace Element Content in the Seeds, Pulp, and Peel of Mashui Oranges Using Microwave Digestion and ICP-MS Analysis.

    PubMed

    Chen, Lingyun; Shen, Mei; Ma, Ande; Han, Weili

    2018-03-01

    Fresh Mashui orange samples were pretreated with microwave digestion using an HNO 3 -H 2 O 2 system. The levels of Mg, K, Ca, Fe, Mn, Cu, Zn, As, Cd, and Pb in the seeds, pulp, and peel were then determined using inductively coupled plasma mass spectrometry (ICP-MS) combined with collision cell technology (CCT) and kinetic energy discrimination (KED). The standard curve coefficient of determinations of the ten tested elements were between 0.9995 and 0.9999. The instrument detection limit was between 0.112 ng/L and 3.05 ng/mL. The method detection limit was between 0.0281 and 763 ng/g. The average recovery rate was between 85.0 and 117%. The current results showed that Mashui oranges are rich in three elements, namely Mg, K, and Ca. The concentrations of K and Ca were significantly higher than that of Mg in the peel. The content of K was the highest in the seeds. Fe, Mn, Cu, and Zn had the second highest concentrations, and Fe was the highest in the seeds, while Cu was the lowest in the peel. As, Cd, and Pb (hazardous elements) had the lowest concentrations of all the tested elements.

  17. Advanced functional materials in solid phase extraction for ICP-MS determination of trace elements and their species - A review.

    PubMed

    He, Man; Huang, Lijin; Zhao, Bingshan; Chen, Beibei; Hu, Bin

    2017-06-22

    For the determination of trace elements and their species in various real samples by inductively coupled plasma mass spectrometry (ICP-MS), solid phase extraction (SPE) is a commonly used sample pretreatment technique to remove complex matrix, pre-concentrate target analytes and make the samples suitable for subsequent sample introduction and measurements. The sensitivity, selectivity/anti-interference ability, sample throughput and application potential of the methodology of SPE-ICP-MS are greatly dependent on SPE adsorbents. This article presents a general overview of the use of advanced functional materials (AFMs) in SPE for ICP-MS determination of trace elements and their species in the past decade. Herein the AFMs refer to the materials featuring with high adsorption capacity, good selectivity, fast adsorption/desorption dynamics and satisfying special requirements in real sample analysis, including nanometer-sized materials, porous materials, ion imprinting polymers, restricted access materials and magnetic materials. Carbon/silica/metal/metal oxide nanometer-sized adsorbents with high surface area and plenty of adsorption sites exhibit high adsorption capacity, and porous adsorbents would provide more adsorption sites and faster adsorption dynamics. The selectivity of the materials for target elements/species can be improved by using physical/chemical modification, ion imprinting and restricted accessed technique. Magnetic adsorbents in conventional batch operation offer unique magnetic response and high surface area-volume ratio which provide a very easy phase separation, greater extraction capacity and efficiency over conventional adsorbents, and chip-based magnetic SPE provides a versatile platform for special requirement (e.g. cell analysis). The performance of these adsorbents for the determination of trace elements and their species in different matrices by ICP-MS is discussed in detail, along with perspectives and possible challenges in the future

  18. Measurement of very low amounts of arsenic in soils and waters: is ICP-MS the indispensable analytical tool?

    NASA Astrophysics Data System (ADS)

    López-García, Ignacio; Marín-Hernández, Juan Jose; Perez-Sirvent, Carmen; Hernandez-Cordoba, Manuel

    2017-04-01

    The toxicity of arsenic and its wide distribution in the nature needs nowadays not to be emphasized, and the convenience of reliable analytical tools for arsenic determination at very low levels is clear. Leaving aside atomic fluorescence spectrometers specifically designed for this purpose, the task is currently carried out by using inductively coupled plasma mass spectrometry (ICP-MS), a powerful but expensive technique that is not available in all laboratories. However, as the recent literature clearly shows, a similar or even better analytical performance for the determination of several elements can be achieved by replacing the ICP-MS instrument by an AAS spectrometer (which is commonly present in any laboratory and involves low acquisition and maintenance costs) provided that a simple microextraction step is used to preconcentrate the sample. This communication reports the optimization and results obtained with a new analytical procedure based on this idea and focused to the determination of very low concentrations of arsenic in waters and extracts from soils and sediments. The procedure is based on a micro-solid phase extraction process for the separation and preconcentration of arsenic that uses magnetic particles covered with silver nanoparticles functionalized with the sodium salt of 2-mercaptoethane-sulphonate (MESNa). This composite is obtained in an easy way in the laboratory. After the sample is treated with a low amount (only a few milligrams) of the magnetic material, the solid phase is separated by means of a magnetic field, and then introduced into an electrothermal atomizer (ETAAS) for arsenic determination. The preconcentration factor is close to 200 with a detection limit below 0.1 µg L-1 arsenic. Speciation of As(III) and As(V) can be achieved by means of two extractions carried out at different acidity. The results for total arsenic are verified using certified reference materials. The authors are grateful to the Comunidad Autonóma de la

  19. Development of a large volume injection method using a programmed temperature vaporization injector - gas chromatography hyphenated to ICP-MS for the simultaneous determination of mercury, tin and lead species at ultra-trace levels in natural waters.

    PubMed

    Terán-Baamonde, J; Bouchet, S; Tessier, E; Amouroux, D

    2018-04-27

    The current EU legislation lays down Environmental Quality Standards (EQS) for 45 priority substances in surface waters; among them levels for (organo)metallic species of Hg, Sn and Pb are set between ng L -1 (for Hg and Sn) and μg L -1 (for Pb). To date, only a few analytical methods can reach these very restrictive limits and there is thus a need for comprehensive methods able to analyze these species down to these levels in natural waters. The aim of this work was to develop an online automated pre-concentration method using large volume injections with a Programmed Temperature Vaporization (PTV) injector fitted with a sorbent packed liner coupled to GC-ICP-MS to further improve the detection limits associated to this well-established method. The influence of several parameters such as the PTV transfer temperature and time, carrier gas flow rate and amount of packing material was investigated. Finally, the maximum volume injected through single or multiple injection modes was optimized to obtain the best compromise between chromatographic resolution and sensitivity. After optimization, very satisfactory results in terms of absolute and methodological detection limits were achieved, down to the pg L -1 level for all species studied. The potential of the method was exemplified by determining the concentrations of organometallic compounds in unpolluted river waters samples from the Adour river basin (SW France) and results were compared with conventional (splitless) GC-ICP-MS. The strength of this analytical method lies in the low detection limits reached for the simultaneous analysis of a wide group of organometallic compounds, and the potential to transfer this method to other gas chromatographic applications with inherent lower sensitivity. Copyright © 2018 Elsevier B.V. All rights reserved.

  20. Evaluation of the inorganic selenium biotransformation in selenium-enriched yogurt by HPLC-ICP-MS.

    PubMed

    Alzate, Adriana; Cañas, Benito; Pérez-Munguía, Sandra; Hernández-Mendoza, Hector; Pérez-Conde, Concepción; Gutiérrez, Ana Maria; Cámara, Carmen

    2007-11-28

    Selenium is an essential element in the human diet. Interestingly, there has been an increased consumption of dietary supplements containing this element in the form of either inorganic or organic compounds. The effect of using selenium as a dietary supplement in yogurt has been evaluated. For this purpose, different concentrations of inorganic Se (ranging from 0.2 to 5000 microg g(-1)) have been added to milk before the fermentation process. Biotransformation of inorganic Se into organic species has been carefully evaluated by ion-exchange, reversed-phase, or size-exclusion chromatography, coupled to inductively coupled plasma mass spectrometry (ICP-MS). Yogurt fermentation in the presence of up to 2 microg g(-1) of Se(IV) produces a complete incorporation of this element into proteins as has been demonstrated applying a dialysis procedure. Analysis by SEC-ICP-MS showed that most of them have a molecular mass in the range of 30-70 kDa. Species determination after enzymatic hydrolysis has allowed the identification of Se-cystine using two different chromatographic systems. The biotransformation process that takes place during yogurt fermentation is very attractive because yogurt can act as a source of selenium supplementation.

  1. 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.

  2. 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.

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

    PubMed

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

    2012-06-01

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

  4. 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.

  5. Analysis of gold(I/III)-complexes by HPLC-ICP-MS demonstrates gold(III) stability in surface waters.

    PubMed

    Ta, Christine; Reith, Frank; Brugger, Joël; Pring, Allan; Lenehan, Claire E

    2014-05-20

    Understanding the form in which gold is transported in surface- and groundwaters underpins our understanding of gold dispersion and (bio)geochemical cycling. Yet, to date, there are no direct techniques capable of identifying the oxidation state and complexation of gold in natural waters. We present a reversed phase ion-pairing HPLC-ICP-MS method for the separation and determination of aqueous gold(III)-chloro-hydroxyl, gold(III)-bromo-hydroxyl, gold(I)-thiosulfate, and gold(I)-cyanide complexes. Detection limits for the gold species range from 0.05 to 0.30 μg L(-1). The [Au(CN)2](-) gold cyanide complex was detected in five of six waters from tailings and adjacent monitoring bores of working gold mines. Contrary to thermodynamic predictions, evidence was obtained for the existence of Au(III)-complexes in circumneutral, hypersaline waters of a natural lake overlying a gold deposit in Western Australia. This first direct evidence for the existence and stability of Au(III)-complexes in natural surface waters suggests that Au(III)-complexes may be important for the transport and biogeochemical cycling of gold in surface environments. Overall, these results show that near-μg L(-1) enrichments of Au in environmental waters result from metastable ligands (e.g., CN(-)) as well as kinetically controlled redox processes leading to the stability of highly soluble Au(III)-complexes.

  6. Lead isotope ratios in lichen samples evaluated by ICP-ToF-MS to assess possible atmospheric pollution sources in Havana, Cuba.

    PubMed

    Alvarez, Alfredo Montero; Estévez Alvarez, Juan R; do Nascimento, Clístenes Williams Araújo; González, Iván Pupo; Rizo, Oscar Díaz; Carzola, Lázaro Lima; Torres, Roberto Ayllón; Pascual, Jorge Gómez

    2017-01-01

    Epiphytic lichens, collected from 119 sampling sites grown over "Roistonea Royal Palm" trees, were used to assess the spatial distribution pattern of lead (Pb) and identify possible pollution sources in Havana (Cuba). Lead concentrations in lichens and topsoils were determined by flame atomic absorption spectrophotometry and inductively coupled plasma (ICP) atomic emission spectrometry, respectively, while Pb in crude oils and gasoline samples were measured by ICP-time of flight mass spectrometry (ICP-ToF-MS). Lead isotopic ratios measurements for lichens, soils, and crude oils were obtained by ICP-ToF-MS. We found that enrichment factors (EF) reflected a moderate contamination for 71% of the samples (EF > 10). The 206 Pb/ 207 Pb ratio values for lichens ranged from 1.17 to 1.20 and were a mixture of natural radiogenic and industrial activities (e.g., crude oils and fire plants). The low concentration of Pb found in gasoline (<7.0 μg L -1 ) confirms the official statement that leaded gasoline is no longer used in Cuba.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  8. 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

  9. 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

  10. 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

  11. Elemental profiling and geographical differentiation of Ethiopian coffee samples through inductively coupled plasma-optical emission spectroscopy (ICP-OES), ICP-mass spectrometry (ICP-MS) and direct mercury analyzer (DMA).

    PubMed

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

    2016-12-01

    This study was aimed to establish the elemental profiling and provenance of coffee samples collected from eleven major coffee producing regions of Ethiopia. A total of 129 samples were analyzed for forty-five elements using inductively coupled plasma (ICP)-optical emission spectroscopy (OES), ICP-mass spectrometry (MS) and direct mercury analyzer (DMA). Among the macro elements, K showed the highest levels whereas Fe was found to have the lowest concentration values. In all the samples, Ca, K, Mg, P and S contents were statistically significant (p<0.05). Micro elements showed the concentrations order of: Mn>Cu>Sr>Zn>Rb>Ni>B. Contents of the trace elements were lower than the permissible standard values. Inter-regions differentiation by cluster analysis (CA), linear discriminant analysis (LDA) and principal component analysis (PCA) showed that micro and trace elements are the best chemical descriptors of the analyzed coffee samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. [The matrix effects of organic acid compounds in ICP-MS].

    PubMed

    Nie, Xi-Du; He, Xiao-Mei; Li, Li-Bo; Xie, Hua-Lin

    2007-07-01

    The matrix effects arising from oxalic acid, lactic acid, tartaric acid and citric acid in inductively coupled plasma mass spectrometry (ICP-MS) were investigated. It has been proved that the sensitivity of analytes can be significantly enhanced by adding small amounts of organic acid compounds with adjusted nebulizer gas flow-rate, especially for the elements with ionization potential between 9 and 11 eV. The tartaric acid has higher enhancement effect on the signal intensity of the hard-to-ionize elements than oxalic acid, lactic acid and citric acid. The mechanism of the enhancement was investigated. The method has been used to determine Be, Zn, As, Se, Sb and Hg in water standard reference materials (SRM). The analytical results are very close to the certified values.

  13. Ultra-trace determination of Strontium-90 in environmental soil samples from Qatar by collision/reaction cell-inductively coupled plasma mass spectrometry (CRC-ICP-MS/MS)

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

    Al-Meer, S. H.; Amr, M. A.; Helal, A.I.

    Because of the very low level of {sup 90}Sr in the environmental soil samples and its determination by beta counting may take several weeks, we developed a procedure for ultra-trace determination of {sup 90}Sr using collision reaction cell-inductively coupled plasma tandem mass spectrometry (CRC-ICP-MS/MS, Agilent 8800). Soil samples were dried at 105 deg. C and then heated in a furnace at 550 deg. C to remove any organics present. 500 g of each soil samples were aliquoted into 2000 ml glass beakers. Each Soils samples were soaked in 2 ppm Sr solution carrier to allow determination of chemical yield. Themore » solid to liquid ratio was 1:1. Finally the soil samples were dried at 105 deg. C. Five hundred milliliters concentrated nitric acid and 250 ml hydrochloric acid volumes were added on 500 g soil samples. The samples were digested on hot plate at 80 deg. C to prevent spraying with continuous manual mixing. The leachate solution was separated. The solids were rinsed with 500 ml deionized water, warmed on a hot plate and the leachate plus previous leachate were filtered and the total volume was reduced to 500 ml by evaporation. Final leachate volume was transferred to a centrifuge tubes. The centrifuge tubes were centrifuged at 3,500 rpm for 10 min. The leachate was transferred to a 1 L beaker and heated on a hot plate to evaporate the leachate to dryness. The reside was re-dissolved in 100 ml of 2% HNO{sub 3} and reduced by evaporation to 10 mL. The solution was measured directly by CRC-ICP-MS/MS by setting the first quadruple analyzer to m/z 90 and introducing oxygen gas into the reaction cell for elimination isobar interference from zirconium-90. The method was validated by measurements of standard reference materials and applied on environmental soil samples. The overall time requirement for the measurement of strontium-90 by CRC-ICP-MS/MS is 2 days, significantly shorter than any radioanalytical protocol currently available. (authors)« less

  14. Two-dimensional HPLC coupled to ICP-MS and electrospray ionisation (ESI)-MS/MS for investigating the bioavailability in vitro of arsenic species from edible seaweed.

    PubMed

    Garcia-Sartal, Cristina; Taebunpakul, Sutthinun; Stokes, Emma; Barciela-Alonso, María del Carmen; Bermejo-Barrera, Pilar; Goenaga-Infante, Heidi

    2012-04-01

    Edible seaweed consumption is a route of exposure to arsenic. However, little attention has been paid to estimate the bioaccessibility and/or bioavailability of arsenosugars in edible seaweed and their possible degradation products during gastrointestinal digestion. This work presents first use of combined inductively coupled plasma mass spectroscopy (ICP-MS) with electrospray ionization tandem mass spectrometry (ESI-MS/MS) with two-dimensional HPLC (size exclusion followed by anion exchange) to compare the qualitative and quantitative arsenosugars speciation of different edible seaweed with that of their bioavailable fraction as obtained using an in vitro gastrointestinal digestion procedure. Optimal extraction conditions for As species from four seaweed namely kombu, wakame, nori and sea lettuce were selected as a compromise between As extraction efficiency and preservation of compound identity. For most investigated samples, the use of ammonium acetate buffer as extractant and 1 h sonication in a water bath followed by HPLC-ICP-MS resulted in 40-61% of the total As to be found in the buffered aqueous extract, of which 86-110% was present as arsenosugars (glycerol sugar, phosphate sugar and sulfonate sugar for wakame and kombu and glycerol sugar and phosphate sugar for nori). The exception was sea lettuce, for which the arsenosugar fraction (glycerol sugar, phosphate sugar) only comprised 44% of the total extracted As. Interestingly, the ratio of arsenobetaine and dimethylarsinic acid to arsenosugars in sea lettuce extracts seemed higher than that for the rest of investigated samples. After in vitro gastrointestinal digestion, approximately 11-16% of the total As in the solid sample was found in the dialyzates with arsenosugars comprising 93-120% and 41% of the dialyzable As fraction for kombu, wakame, nori and sea lettuce, respectively. Moreover, the relative As species distribution in seaweed-buffered extracts and dialyzates was found to be very similar

  15. Simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate in welding fume alkaline extracts by HPLC-ICP-MS.

    PubMed

    Ščančar, Janez; Berlinger, Balázs; Thomassen, Yngvar; Milačič, Radmila

    2015-09-01

    A novel analytical procedure was developed for the simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate by anion-exchange high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Linear gradient elution from 100% water to 100% 0.7 M NaCl was applied for chromatographic separation of metal species. In standard aqueous solution at neutral pH molybdate, tungstate and vanadate exist in several aqueous species, while chromate is present as a single CrO4(2-) species. Consequently, only chromate can be separated from this solution in a sharp chromatographic peak. For obtaining sharp chromatographic peaks for molybdate, tungstate and vanadate, the pH of aqueous standard solutions was raised to 12. At highly alkaline conditions single CrO4(2-), MoO4(2-) and WO4(2-) are present and were eluted in sharp chromatographic peaks, while VO4(3-) species, which predominates at pH 12 was eluted in slightly broaden peak. In a mixture of aqueous standard solutions (pH 12) chromate, molybdate, tungstate and vanadate were eluted at retention times from 380 to 420 s, 320 to 370 s, 300 to 350 s and 240 to 360 s, respectively. Eluted species were simultaneously detected on-line by ICP-MS recording m/z 52, 95, 182 and 51. The developed procedure was successfully applied to the analysis of leachable concentrations of chromate, molybdate, tungstate and vanadate in alkaline extracts (2% NaOH+3% Na2CO3) of manual metal arc (MMA) welding fumes loaded on filters. Good repeatability and reproducibility of measurement (RSD±3.0%) for the investigated species were obtained in both aqueous standard solutions (pH 12) and in alkaline extracts of welding fumes. Low limits of detection (LODs) were found for chromate (0.02 ng Cr mL(-1)), molybdate (0.1 ng Mo mL(-1)), tungstate (0.1 ng W mL(-1)) and vanadate (0.2 ng V mL(-1)). The accuracy of analytical procedure for the determination of chromate was checked by analysis of

  16. [Application of ICP-MS to Detect Rare Earth Elements in Three Economic Macroalgaes in China].

    PubMed

    Zhao, Yan-fang; Shang, De-rong; Zhai, Yu-xiu; Ning, Jin-song; Ding, Hai-yan; Sheng, Xiao-feng

    2015-11-01

    In order to investigate the content and distribution of rare earth elements (REE) in main economic macroalgaes in our country, fifteen rare earth elements in three economic macroalgaes (including 30 samples of kelp, 30 samples of laver and 15 samples of Enteromorpha) were detected using ICP-MS method. Results showed that the total content of REE in different species of macroalgaes was different. The highest total content of REE was in Enteromorpha (16,012.0 ng · g⁻¹), while in kelp and laver, the total REE was similar for two macroalgaes (3887.4 and 4318.1 ng · g⁻¹ respectively). The content of fifteen rare earth elements in kelp ranged from 7.9 to 1496.4 ng · g⁻¹; in laver, it ranged from 8.2 to 1836.6 ng · g⁻¹. For Enteromorpha, the concentration of 15 rare earth elements were between 19.2 and 6014.5 ng · g⁻¹. In addition, the content and distribution of different rare earth elements in different macroalgaes was also different. For kelp, the highest content of REE was Ce (1 496.4 ng · g⁻¹), and the second was La (689.1 ng · g⁻¹). For laver, the highest was Y (1836.6 ng · g⁻¹), and the second was Ce (682.2 ng · g⁻¹). For Enteromorpha, the highest was Ce (6014.5 ng · g⁻¹), and the second was La (2902.9 ng · g⁻¹). Present results also showed that three macroalgaes accumulated the light rare earth elements much more than the high rare earth elements. The light rare earth elements occupied 90.9%, 87.3% and 91.1% for kelp, laver and Enteromorpha respectively. The result that the Enteromorpha had high content of rare earth elements could provide important support for opening new research directions for the utilization of Enteromorpha.

  17. 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

  18. Direct determination of trace refractory elements in human serum by ETV-ICP-MS with in-situ matrix removal.

    PubMed

    Li, Shengqing; Hu, Bin; Jiang, Zucheng; Chen, Rui

    2004-08-01

    A method for in-situ removal of matrix is proposed for direct determination of trace refractory elements in human serum by ETV-ICP-MS with the use of poly(tetrafluoroethylene) (PTFE) as fluorinating reagent. Attention has been paid to investigating the vaporization behavior both of refractory elements of interest and of matrix elements (Na, K, Ca, Mg, Cl, S, and P) in a graphite furnace with the PTFE modifier present or not. It was shown that potential interferences from the organic and inorganic matrices in the serum sample could be eliminated or reduced to a negligible level by appropriate dilution of the serum and deliberate optimization of the ETV temperature program. The proposed method has been applied to the direct simultaneous determination of V, Cr, Mo, Ba, La, Ce, and W in human serum. The limits of detection for fivefold diluted serum were 0.18 (V), 0.229 (Cr), 0.050 (Mo), 0.328 (Ba), 0.031 (La), 0.038 (Ce), and 0.019 ng mL(-1) (W), respectively, and the relative standard deviations of the method were in the range 4-15% (2 ng mL(-1) in serum, n=3).

  19. 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.

  20. Determination of mercury in SRM crude oils and refined products by isotope dilution cold vapor ICP-MS using closed-system combustion.

    PubMed

    Kelly, W Robert; Long, Stephen E; Mann, Jacqueline L

    2003-07-01

    Mercury was determined by isotope dilution cold-vapor inductively coupled plasma mass spectrometry (ID-CV-ICP-MS) in four different liquid petroleum SRMs. Samples of approximately 0.3 g were spiked with stable (201)Hg and wet ashed in a closed system (Carius tube) using 6 g of high-purity nitric acid. Three different types of commercial oils were measured: two Texas crude oils, SRM 2721 (41.7+/-5.7 pg g(-1)) and SRM 2722 (129+/-13 pg g(-1)), a low-sulfur diesel fuel, SRM 2724b (34+/-26 pg g(-1)), and a low-sulfur residual fuel oil, SRM 1619b (3.5+/-0.74 ng g(-1)) (mean value and 95% CI). The Hg values for the crude oils and the diesel fuel are the lowest values ever reported for these matrices. The method detection limit, which is ultimately limited by method blank uncertainty, is approximately 10 pg g(-1) for a 0.3 g sample. Accurate Hg measurements in petroleum products are needed to assess the contribution to the global Hg cycle and may be needed in the near future to comply with reporting regulations for toxic elements.

  1. 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).

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. 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

  7. Direct separation of boron from Na- and Ca-rich matrices by sublimation for stable isotope measurement by MC-ICP-MS.

    PubMed

    Wang, Bo-Shian; You, Chen-Feng; Huang, Kuo-Fang; Wu, Shein-Fu; Aggarwal, Suresh Kumar; Chung, Chuan-Hsiung; Lin, Pei-Ying

    2010-09-15

    An improved technique for precise and accurate determination of boron isotopic composition in Na-rich natural waters (groundwater, seawater) and marine biogenic carbonates was developed. This study used a 'micro-sublimation' technique to separate B from natural sample matrices in place of the conventional ion-exchange extraction. By adjusting analyte to appropriate pH, quantitative recovery of boron can be achieved (>98%) and the B procedural blank is limited to <8 pg. An additional mass bias effect in MC-ICP-MS was observed which could not be improved via the standard-sample-standard bracketing or the 'pseudo internal' normalization by Li. Therefore a standard other than NBS SRM 951 was used to monitor plasma condition in order to maintain analytical accuracy. An isotope cross-calibration with results from TIMS shows that the space-charge mass bias on MC-ICP-MS can be successfully corrected using off-line mathematical manipulation. Several reference materials, including the seawater IAPSO and two groundwater standards IAEA-B-2 and IAEA-B-3, were used to validate this approach. We found that the delta(11)B of the reference coral JCp-1 was 24.22+/-0.28 per thousand, corresponding to seawater pH based on the coral delta(11)B-pH function. Copyright (c) 2010 Elsevier B.V. All rights reserved.

  8. 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

  9. 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

  10. 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.

  11. ICP-MS based methods to characterize nanoparticles of TiO2 and ZnO in sunscreens with focus on regulatory and safety issues.

    PubMed

    Bocca, Beatrice; Caimi, Stefano; Senofonte, Oreste; Alimonti, Alessandro; Petrucci, Francesco

    2018-07-15

    This study sought to develop analytical methods to characterize titanium dioxide (TiO 2 ) and zinc oxide (ZnO) nanoparticles (NPs), including the particle size distribution and concentration, in cream and spray sunscreens with different sun protection factor (SPF). The Single Particle Inductively Coupled Plasma-Mass Spectrometry (SP ICP-MS) was used as screening and fast method to determine particles size and number. The Asymmetric Flow-Field Flow Fractionation (AF4-FFF) as a pre-separation technique was on-line coupled to the Multi-Angle Light Scattering (MALS) and ICP-MS to determine particle size distributions and size dependent multi-elemental concentration. Both methods were optimized in sunscreens in terms of recovery, repeatability, limit of detection and linear dynamic range. Results showed that sunscreens contained TiO 2 particles with an average size of ≤107 nm and also a minor number of ZnO particles sized ≤98 nm. The higher fraction of particles <100 nm was observed in sunscreens with SPF 50+ (ca. 80%); the lower percentage (12-35%) in sunscreens with lower SPF values. Also the higher TiO 2 (up to 24% weight) and ZnO (ca. 0.25% weight) concentrations were found in formulations of SPF 50+. Creamy sunscreens could be considered safe containing TiO 2 and ZnO NPs less than the maximum allowable concentration of 25% weight as set by the European legislation. On the contrary, spray products required additional considerations with regard to the potential inhalation of NPs. The developed methods can contribute to the actual demand for regulatory control and safety assessment of metallic NPs in consumers' products. Copyright © 2018 Elsevier B.V. All rights reserved.

  12. 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.

  13. Use of experimental design for optimisation of the cold plasma ICP-MS determination of lithium, aluminum and iron in soft drinks and alcoholic beverages.

    PubMed

    Bianchi, F; Careri, M; Maffini, M; Mangia, A; Mucchino, C

    2003-01-01

    A sensitive method for the simultaneous determination of (7)Li, (27)Al and (56)Fe by cold plasma ICP-MS was developed and validated. Experimental design was used to investigate the effects of torch position, torch power, lens 2 voltage, and coolant flow. Regression models and desirability functions were applied to find the experimental conditions providing the highest global sensitivity in a multi-elemental analysis. Validation was performed in terms of limits of detection (LOD), limits of quantitation (LOQ), linearity and precision. LODs were 1.4 and 159 ng L(-1) for (7)Li and (56)Fe, respectively; the highest LOD found being that for (27)Al (425 ng L(-1)). Linear ranges of 5 orders of magnitude for Li and 3 orders for Fe were statistically verified for each compound. Precision was evaluated by testing two concentration levels, and good results in terms of both intra-day repeatability and intermediate precision were obtained. RSD values lower than 4.8% at the lowest concentration level were calculated for intra-day repeatability. Commercially available soft drinks and alcoholic beverages contained in different packaging materials (TetraPack, polyethylene terephthalate (PET), commercial cans and glass) were analysed, and all the analytes were detected and quantitated. Copyright 2002 John Wiley & Sons, Ltd.

  14. Determination of plutonium and its isotopic ratio in marine sediment samples using quadrupole ICP-MS with the shield torch system under normal plasma conditions.

    PubMed

    Zheng, Jian; Yamada, Masatoshi; Wang, Zhongliang; Aono, Tatsuo; Kusakabe, Masashi

    2004-06-01

    An analytical method for determining (239)Pu and (240)Pu in marine sediment samples, which uses quadrupole ICP-MS, was developed in this work. A simple anion-exchange chromatography system was employed for the separation and purification of Pu from the sample matrix. A sufficient decontamination factor of 1.4 x 10(4) for U, which interferes with the determination of (239)Pu, was achieved. High sensitivity Pu determination was obtained, which led to an extremely low concentration detection limit of approximately 8 fg/ml (0.019 mBq/ml for (239)Pu; 0.071 mBq/ml for (240)Pu) in a sample solution, or an absolute detection limit of 42 fg in a 5 ml sample solution, by using the shield torch technique. Analytical results for the determination of the (239+240)Pu and the (240)Pu/(239)Pu ratio in IAEA 368 (ocean sediment) reference material indicated that the accuracy of the method was satisfactory. The method developed was successfully applied to a study of Pu behavior in the sediments from Sagami Bay, Japan. The observed high (240)Pu/(239)Pu ratio in the sediment core indicated that there was additional Pu input derived from close-in fallout in addition to the global fallout.

  15. 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.

  16. 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

  17. 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

  18. 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.

  19. Translocation of silver nanoparticles in the ex vivo human placenta perfusion model characterized by single particle ICP-MS.

    PubMed

    Vidmar, Janja; Loeschner, Katrin; Correia, Manuel; Larsen, Erik H; Manser, Pius; Wichser, Adrian; Boodhia, Kailen; Al-Ahmady, Zahraa S; Ruiz, Jaimé; Astruc, Didier; Buerki-Thurnherr, Tina

    2018-06-15

    With the extensive use of silver nanoparticles (AgNPs) in various consumer products their potential toxicity is of great concern especially for highly sensitive population groups such as pregnant women and even the developing fetus. To understand if AgNPs are taken up and cross the human placenta, we studied their translocation and accumulation in the human ex vivo placenta perfusion model by single particle ICP-MS (spICP-MS). The impact of different surface modifications on placental transfer was assessed by AgNPs with two different modifications: polyethylene glycol (AgPEG NPs) and sodium carboxylate (AgCOONa NPs). AgNPs and ionic Ag were detected in the fetal circulation in low but not negligible amounts. Slightly higher Ag translocation across the placental barrier for perfusion with AgPEG NPs and higher AgNP accumulation in placental tissue for perfusion with AgCOONa NPs were observed. Since these AgNPs are soluble in water, we tried to distinguish between the translocation of dissolved and particulate Ag. Perfusion with AgNO3 revealed the formation of Ag containing NPs in both circulations over time, of which the amount and their size in the fetal circulation were comparable to those from perfusion experiments with both AgNP types. Although we were not able to clarify whether intact AgNPs and/or Ag precipitates from dissolved Ag cross the placental barrier, our study highlights that uptake of Ag ions and/or dissolution of AgNPs in the tissue followed by re-precipitation in the fetal circulation needs to be considered as an important pathway in studies of AgNP translocation across biological barriers.

  20. The potential of on-line continuous leach ICP-MS analysis for linking trace elements to mineralogy

    NASA Astrophysics Data System (ADS)

    Roskam, Gerlinde; Verheul, Marc; Moraetis, Daniel; Giannakis, George; van Gaans, Pauline

    2014-05-01

    A set of five soil samples was subjected to an on-line continuous leach inductively coupled plasma mass spectrometry experiment, with progressively reactive solvents (0.01M CaCl2, 0.1 M HNO3, 1M HNO3, 4M HNO3) Each sample was packed in a quartz tube (Ø= 1 cm, length 2 cm) and diluted 1:1 with acid washed quartz to prevent clogging. The gas that was produced during the extraction was removed by leading the effluent into a small container, from where the sample was directly pumped into the ICP-MS. 115In was used as an internal standard. Continuous leach experiments have the advantage of real time (every 2 seconds) full elemental analysis. Mineral breakdown reactions can be monitored via the major elements. The trace elements associated with the minerals are monitored simultaneously, thus eliminating the uncertainties of host mineral-trace element combinations in traditional off-line sequential extractions. The continuous leach experimental data are correlated to XRD-results for mineralogy and total elemental concentrations. The soil samples used were collected from different sites in the Koiliaris River watershed, Crete, Greece 1). The selection of the sites was based on variability in bedrock (limestone, metamorphic and alluvial sediments) and current land use (grape farming, olive trees). Soils were sampled at two depths: at the surface and just above the bedrock. No large differences in the major elements between the two depths were measured. To provide background to the on-line sequential data, also total concentrations of the major elements were analysed by XRF and the mineralogy was analysed by XRD. The fraction <2mm was sieved and digested with HF, HClO4 and HNO3 for additional trace element analysis. 1) See related abstract Roskam et al., 2014: REE profiles in continuous leach ICP-MS (CL-ICP-MS) experiments in soil, linked to REE profiles in surface water in the Koiliaris River Critical Zone Observatory (CZO), Crete, Greece.

  1. 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.

  2. ICP-MS with hexapole collision cell for isotope ratio measurements of Ca, Fe, and Se.

    PubMed

    Boulyga, S F; Becker, J S

    2001-07-01

    To avoid mass interferences on analyte ions caused by argon ions and argon molecular ions via reactions with collision gases, an rf hexapole filled with helium and hydrogen has been used in inductively coupled plasma mass spectrometry (ICP-MS), and its performance has been studied. Up to tenfold improvement in sensitivity was observed for heavy elements (m > 100 u), because of better ion transmission through the hexapole ion guide. A reduction of argon ions Ar+ and the molecular ions of argon ArX+ (X = O, Ar) by up to three orders of magnitude was achieved in a hexapole collision cell of an ICP-MS ("Platform ICP", Micromass, Manchester, UK) as a result of gas-phase reactions with hydrogen when the hexapole bias (HB) was set to 0 V; at an HB of 1.6 V argon, and argon-based ions of masses 40 u, 56 u, and 80 u, were reduced by approximately four, two, and five orders of magnitude, respectively. The signal-to-noise ratio 80Se/ 40Ar2+ was improved by more than five orders of magnitude under optimized experimental conditions. Dependence of mass discrimination on collision-cell properties was studied in the mass range 10 u (boron) to 238 u (uranium). Isotopic analysis of the elements affected by mass-spectrometric interference, Ca, Fe, and Se, was performed using a Meinhard nebulizer and an ultrasonic nebulizer (USN). The measured isotope ratios were comparable with tabulated values from IUPAC. Precision of 0.26%, 0.19%, and 0.12%, respectively, and accuracy of 0.13% 0.25%, and 0.92%, respectively, was achieved for isotope ratios 44Ca/ 40Ca and 56Fe/57Fe in 10 microg L(-1) solution nebulized by means of a USN and for 78Se/80Se in 100 microg L(-1) solution nebulized by means of a Meinhard nebulizer.

  3. Antidepressants detection and quantification in whole blood samples by GC-MS/MS, for forensic purposes.

    PubMed

    Truta, Liliana; Castro, André L; Tarelho, Sónia; Costa, Pedro; Sales, M Goreti F; Teixeira, Helena M

    2016-09-05

    Depression is among the most prevalent psychiatric disorders of our society, leading to an increase in antidepressant drug consumption that needs to be accurately determined in whole blood samples in Forensic Toxicology Laboratories. For this purpose, this work presents a new gas chromatography tandem mass spectrometry (GC-MS/MS) method targeting the simultaneous and rapid determination of 14 common Antidepressants in whole blood: 13 Antidepressants (amitriptyline, citalopram, clomipramine, dothiepin, fluoxetine, imipramine, mianserin, mirtazapine, nortryptiline, paroxetine, sertraline, trimipramine and venlafaxine) and 1 Metabolite (N-desmethylclomipramine). Solid-phase extraction was used prior to chromatographic separation. Chromatographic and MS/MS parameters were selected to improve sensitivity, peak resolution and unequivocal identification of the eluted analyte. The detection was performed on a triple quadrupole tandem MS in selected ion monitoring (SIM) mode in tandem, using electronic impact ionization. Clomipramine-D3 and trimipramine-D3 were used as deutered internal standards. The validation parameters included linearity, limits of detection, lower limit of quantification, selectivity/specificity, extraction efficiency, carry-over, precision and robustness, and followed internationally accepted guidelines. Limits of quantification and detection were lower than therapeutic and sub-therapeutic concentration ranges. Overall, the method offered good selectivity, robustness and quick response (<16min) for typical concentration ranges, both for therapeutic and lethal levels. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Quantitating Iron in Serum Ferritin by Use of ICP-MS

    NASA Technical Reports Server (NTRS)

    Smith, Scott M.; Gillman, Patricia L.

    2003-01-01

    A laboratory method has been devised to enable measurement of the concentration of iron bound in ferritin from small samples of blood (serum). Derived partly from a prior method that depends on large samples of blood, this method involves the use of an inductively-coupled-plasma mass spectrometer (ICP-MS). Ferritin is a complex of iron with the protein apoferritin. Heretofore, measurements of the concentration of serum ferritin (as distinguished from direct measurements of the concentration of iron in serum ferritin) have been used to assess iron stores in humans. Low levels of serum ferritin could indicate the first stage of iron depletion. High levels of serum ferritin could indicate high levels of iron (for example, in connection with hereditary hemochromatosis an iron-overload illness that is characterized by progressive organ damage and can be fatal). However, the picture is complicated: A high level of serum ferritin could also indicate stress and/or inflammation instead of (or in addition to) iron overload, and low serum iron concentration could indicate inflammation rather than iron deficiency. Only when concentrations of both serum iron and serum ferritin increase and decrease together can the patient s iron status be assessed accurately. Hence, in enabling accurate measurement of the iron content of serum ferritin, the present method can improve the diagnosis of the patient s iron status. The prior method of measuring the concentration of iron involves the use of an atomic-absorption spectrophotometer with a graphite furnace. The present method incorporates a modified version of the sample- preparation process of the prior method. First, ferritin is isolated; more specifically, it is immobilized by immunoprecipitation with rabbit antihuman polyclonal antibody bound to agarose beads. The ferritin is then separated from other iron-containing proteins and free iron by a series of centrifugation and wash steps. Next, the ferritin is digested with nitric acid

  5. 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.

  6. 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

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

    PubMed

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

    2003-02-01

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

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

    PubMed

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

    2015-10-01

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

  9. PIXE and ICP-MS Analysis of Andrographis Paniculata Medicinal Plant

    NASA Astrophysics Data System (ADS)

    Chandrasekhar Rao, J.; Naidu, B. G.; Sarita, P.; Srikanth, S.; Naga Raju, G. J.

    2017-08-01

    The concentrations of elements Li, Be, Al, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Ag, Cd, Ba, Pb and U in Andrographis Paniculata medicinal plant used in the treatment of Diabetes Mellitus were determined by using Particle Induced X-ray Emission (PIXE) and Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) techniques. This plant was collected from four different geographical locations in Andhra Pradesh, India in order to assess the regional variation of elemental concentrations. Appreciable levels of K, Ca, Cr, Mn, Cu and Zn determined in this plant can be correlated to the antidiabetic property of Andrographis Paniculata since these elements are known to regulate and potentiate insulin action. Presence of toxic elements As, Cd and Pb necessitates the adoption of precautionary measures while prescribing dosage of the herbal medicine prepared from this plant for the treatment diabetes mellitus.

  10. Separation and identification of selenotrisulfides in epithelial cell homogenates by LC-ICP-MS and LC-ESI-MS after incubation with selenite.

    PubMed

    Gabel-Jensen, Charlotte; Gammelgaard, Bente; Bendahl, Lars; Stürup, Stefan; Jøns, Ole

    2006-02-01

    To elucidate how selenite is metabolised in the intestine after oral intake, it was incubated with homogenized epithelial cells from pigs. When the metabolites were analysed by LC-ICP-MS, two major selenium metabolites were separated in the supernatant from the homogenate. These metabolites were formed instantly but disappeared within 15 min. No other selenium-containing compounds appeared during this time. Hence, the secondary reaction products were either volatilised or precipitated. To verify the identity of the compounds, a larger amount of selenite was incubated with epithelial cells. The presence of Cys-Se-SG and GS-Se-SG was verified by LC-ESI-MS. Selenotrisulfides were synthesized by reaction of L-cysteine and L-glutathione with sodium selenite. The reaction mixture contained three main products: selenodicysteine (Cys-Se-Cys), selenocysteine glutathione (Cys-Se-SG), and selenodiglutathione (GS-Se-SG). The two transient selenium compounds in the epithelial cell incubation mixture co-eluted with the synthesized Cys-Se-SG and GS-Se-SG, respectively. The identities of these compounds were verified by LC-ESI-MS. Hence, these selenium metabolites have now been identified by ESI-MS after isolation from epithelial cells.

  11. Graphene nanosheet mediated MALDI-MS (GN-MALDI-MS) for rapid, in situ detection of intact incipient biofilm on material surfaces.

    PubMed

    Wu, Bo Sgum; Gopal, Judy; Hua, Pei-Yang; Wu, Hui-Fen

    2016-09-01

    Detection is the first step to efficient treatment, therefore early detection of biofilm gains paramount importance for the initiation of mitigation protocols. A systematic study was conducted to detect the biofilm formation (1h to 2month period) on aluminium, titanium surfaces and their corresponding oxide film surfaces. The limit of detection (LOD) in case of traditional MALDI-MS was limited to a 6h old biofilm. Whereas, in case of the Graphene nanosheet mediated MALDI-MS (GN-MALDI-MS) approach, early detection of the biofilm was demonstrated to be 1h on titanium surfaces and 3h for Al surfaces. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Simultaneous quantification of 17 trace elements in blood by dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS) equipped with a high-efficiency sample introduction system.

    PubMed

    D'Ilio, S; Violante, N; Di Gregorio, M; Senofonte, O; Petrucci, F

    2006-10-10

    A quadrupole inductively coupled plasma mass spectrometer (Q-ICP-MS) equipped with a dynamic reaction cell (DRC) and coupled with a desolvating nebulization system (APEX-IR) was employed to determine 17 elements (Al, As, Ba, Cd, Co, Cr, Li, Mn, Mo, Ni, Pb, Sb, Se, Sn, Sr, V, and Zr) in blood samples. Ammonia (for Al, Cr, Mn, and V) and O2 (for As and Se) were used as reacting gases. Selection of the best flow rate of the gases and optimization of the quadrupole dynamic bandpass tuning parameter (RPq) were carried out, using digested blood diluted 1+9 with deionized water and spiked with 1 microg L(-1) of Al, Cr, Mn, V and 5 microgL(-1) of As and Se. Detection limits were determined in digested blood using the 3sigma criterion. The desolvating system allowed a sufficient sensitivity to be achieved to determine elements at levels of ng L(-1) without detriment of signal stability. The accuracy of the method was tested with the whole blood certified reference material (CRM), certified for Al, As, Cd, Co, Cr, Mn, Mo, Ni, Pb, Sb, Se, and V, and with indicative values for Ba, Li, Sn, Sr, and Zr. The addition calibration approach was chosen for analysis. In order to confirm the DRC data, samples were also analyzed by means of sector field inductively coupled plasma mass spectrometry (SF-ICP-MS), operating in medium (m/Deltam=4000) and high (m/Deltam=10,000) resolution mode and achieving a good agreement between the two techniques.

  13. Determination of aluminium in groundwater samples by GF-AAS, ICP-AES, ICP-MS and modelling of inorganic aluminium complexes.

    PubMed

    Frankowski, Marcin; Zioła-Frankowska, Anetta; Kurzyca, Iwona; Novotný, Karel; Vaculovič, Tomas; Kanický, Viktor; Siepak, Marcin; Siepak, Jerzy

    2011-11-01

    The paper presents the results of aluminium determinations in ground water samples of the Miocene aquifer from the area of the city of Poznań (Poland). The determined aluminium content amounted from <0.0001 to 752.7 μg L(-1). The aluminium determinations were performed using three analytical techniques: graphite furnace atomic absorption spectrometry (GF-AAS), inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The results of aluminium determinations in groundwater samples for particular analytical techniques were compared. The results were used to identify the ascent of ground water from the Mesozoic aquifer to the Miocene aquifer in the area of the fault graben. Using the Mineql+ program, the modelling of the occurrence of aluminium and the following aluminium complexes: hydroxy, with fluorides and sulphates was performed. The paper presents the results of aluminium determinations in ground water using different analytical techniques as well as the chemical modelling in the Mineql+ program, which was performed for the first time and which enabled the identification of aluminium complexes in the investigated samples. The study confirms the occurrence of aluminium hydroxy complexes and aluminium fluoride complexes in the analysed groundwater samples. Despite the dominance of sulphates and organic matter in the sample, major participation of the complexes with these ligands was not stated based on the modelling.

  14. Multielement analysis of Canadian wines by inductively coupled plasma mass spectrometry (ICP-MS) and multivariate statistics.

    PubMed

    Taylor, Vivien F; Longerich, Henry P; Greenough, John D

    2003-02-12

    Trace element fingerprints were deciphered for wines from Canada's two major wine-producing regions, the Okanagan Valley and the Niagara Peninsula, for the purpose of examining differences in wine element composition with region of origin and identifying elements important to determining provenance. Analysis by ICP-MS allowed simultaneous determination of 34 trace elements in wine (Li, Be, Mg, Al, P, Cl, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Mo, Ag, Cd, Sb, I, Cs, Ba, La, Ce, Tl, Pb, Bi, Th, and U) at low levels of detection, and patterns in trace element concentrations were deciphered by multivariate statistical analysis. The two regions were discriminated with 100% accuracy using 10 of these elements. Differences in soil chemistry between the Niagara and Okanagan vineyards were evident, without a good correlation between soil and wine composition. The element Sr was found to be a good indicator of provenance and has been reported in fingerprinting studies of other regions.

  15. TEM and SP-ICP-MS analysis of the release of silver nanoparticles from decoration of pastry.

    PubMed

    Verleysen, E; Van Doren, E; Waegeneers, N; De Temmerman, P-J; Abi Daoud Francisco, M; Mast, J

    2015-04-08

    Metallic silver is an EU approved food additive referred to as E174. It is generally assumed that silver is only present in bulk form in the food chain. This work demonstrates that a simple treatment with water of "silver pearls", meant for decoration of pastry, results in the release of a subfraction of silver nanoparticles. The number-based size and shape distributions of the single, aggregated, and/or agglomerated particles released from the silver pearls were determined by combining conventional bright-field TEM imaging with semiautomatic particle detection and analysis. In addition, the crystal structure of the particles was studied by electron diffraction and chemical information was obtained by combining HAADF-STEM imaging with EDX spectroscopy and mapping. The TEM results were confirmed by SP-ICP-MS. The representative Ag test nanomaterial NM-300 K was used as a positive control to determine the uncertainty on the measurement of the size and shape of the particles.

  16. 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.

  17. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

  19. 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.

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

    PubMed

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

    2008-01-01

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

  1. 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.

  2. A comparison study on the use of Dowex 1 and TEVA-resin in determination of 99Tc in environmental and nuclear coolant samples in a SIA system with ICP-MS detection.

    PubMed

    Kołacińska, Kamila; Samczyński, Zbigniew; Dudek, Jakub; Bojanowska-Czajka, Anna; Trojanowicz, Marek

    2018-07-01

    This work refers to a comparative study of sorbents widely used in determinations of 99 Tc such as TEVA resin and Dowex 1. Despite having a similar functional group of quaternary amines, both materials represent different chromatographic methods-extraction (TEVA resin) and anion exchange (Dowex 1)-which provides a diverse range of their properties significant in determination of 99 Tc in flow conditions. The comparative tests, carried out in a SIA-LOV (Sequential Injection Analysis-Lab-on-Valve) system combined with mass spectrometric (ICP-MS) detection, considered several factors that are crucial from the standpoint of resin´s utility such as sorption capacity, durability, or selectivity, critical in 99 Tc separation from interferences. The developed and optimized analytical procedure based on the application of the TEVA resin provided determinations of 99 Tc at minimum detectable limit (MDL) 6.00 mBq L -1 in 50 min and has been successfully employed in analyses of samples from nuclear industrial and research units (reactor coolant and sewage) as well as from the river surrounding the nuclear reactor. The method proved to be sufficient for routine analysis of water samples in accordance with EPA standards. The reliability of the method was confirmed in the analysis of the BH standard provided by the NPL for inter-laboratory proficiency tests. The 99 Tc recovery for all real samples was evaluated as 80-100%. Copyright © 2018 Elsevier B.V. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  4. A novel procedure for Rubidium separation and its isotope measurements on geological samples by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Ma, J.; Zhang, Z.; Wei, G.; Zhang, L.

    2017-12-01

    A method including a novel column Rb separation procedure and high-precision Rb isotope measurement in geological materials by using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) in standard-sample-bracketing (SSB) mode has been developed. Sr-Spec resin was employed, in which the distribution coefficients for Rb, K, Ba and Sr are different in nitric acid, to sequentially separate them from the matrix. The dissolved samples were loaded on the column in 3 M HNO3, the main matrix such as Al, Ca, Fe, Mg, Mn and Na were removed by rinsing with 4.5 mL HNO3, Rb and K were then sequentially eluted by 3 M HNO3 in different volumes. After that, Ba was eluted by 8 M HNO3, and Sr was finally eluted by Milli-Q water. This enable us to collect the pure Rb, K, Ba and Sr one by one with recovery close to 100% for their isotopic compositions measurement on MC-ICP-MS. We here focus on Rb isotope measurement. The measurement using MC-ICP-MS yielded an internal precision for δ87Rb of < ± 0.03‰ (2SE), and the external precision was generally better than ± 0.06‰ (2SD) based on the long-term results of the Rb standard solutions NIST SRM 984. A series of geological rock standards, were analyzed using this method, and the results indicate significant Rb isotope differences in different geologic materials. This will provide a powerful tool to investigate Rb isotope fractionation during geological processes.Based on this method, Rb isotope compositions from a basaltic weathering profile were carried out. The data show the lighter Rb (85Rb) isotope is preferentially leached from the weathering profile and remains heavy Rb isotope (87Rb) in the weathered residues during the incipient weathering stage. From the moderate to advanced weathering stage, the significant variations of Rb isotope were observed and multiple factors, such as leaching, adsorption, desorption, and precipitation, should play important role in fractionating Rb isotope.

  5. Determination of cadmium in sediments by diluted HCI extraction and isotope dilution ICP-MS.

    PubMed

    Terán-Baamonde, Javier; Soto-Ferreiro, Rosa-María; Carlosena, Alatzne; Andrade, José-Manuel; Prada, Darío

    2018-08-15

    Isotope dilution ICP-MS is proposed to measure the mass fraction of Cd extracted by diluted HCl in marine sediments, using a fast and simple extraction procedure based on ultrasonic probe agitation. The 111 Cd isotope was added before the extraction to achieve isotope equilibration with native Cd solubilized from the sample. The parameters affecting trueness and precision of isotope ratio measurements were evaluated carefully and subsequently corrected in order to minimize errors; they were: detector dead time, spectral interferences, mass discrimination factor and optimum sample/spike ratio. The mass fraction of Cd extracted was compared with the sum of the certified contents of the three steps of the sequential extraction procedure of the Standards, Measurements and Testing Programme (SM&T) analysing the BCR 701 sediment to validate the method. The certified and measured values agreed, giving a measured / certified mass fraction ratio of 1.05. Further, the extraction procedure itself was studied by adding the enriched isotope after the extraction step, which allowed verifying that analyte losses occurred during this process. Two additional reference sediments with certified total cadmium contents were also analysed. The method provided very good precision (0.9%, RSD) and a low detection limit, 1.8 ng g -1 . The procedural uncertainty budget was estimated following the EURACHEM Guide by means of the 'GUM Workbench' software, obtaining a relative expanded uncertainty of 1.5%. The procedure was applied to determine the bioaccessible mass fraction of Cd in sediments from two environmentally and economically important areas of Galicia (rias of Arousa and Vigo, NW of Spain). Copyright © 2018 Elsevier B.V. All rights reserved.

  6. Selective and eco-friendly method for determination of mercury(II) ions in aqueous samples using an on-line AuNPs-PDMS composite microfluidic device/ICP-MS system.

    PubMed

    Hsu, Keng-Chang; Lee, Cheng-Fa; Tseng, Wei-Chang; Chao, Yu-Ying; Huang, Yeou-Lih

    2014-10-01

    In this study we developed an on-line, eco-friendly, and highly selective method using a gold nanoparticle (AuNP)-coated polydimethylsiloxane (PDMS) composite microfluidic (MF) chip coupled to inductively coupled plasma mass spectrometry (ICP-MS) to separate trace Hg(2+) ions from aqueous samples. Because Hg(2+) ions interact with AuNPs to form Hg-Au complexes, we were able to separate Hg(2+) ions from aqueous samples. We prepared the AuNPs-PDMS composite through in situ synthesis using a PDMS cross-linking agent to both reduce and embed AuNPs onto PDMS microchannels so that no additional reductants were required for either AuNP synthesis or the PDMS surface modification (2% HAuCl4, room temperature, 48 h). To optimize the proposed on-line system, we investigated several factors that influenced the separation of Hg(2+) ions in the AuNPs-PDMS/MF, including adsorption pH, adsorption and elution flow rates, microchannel length, and interferences from coexisting ions. Under optimized conditions (pH 6.0; adsorption/elution flow rates: 0.05/0.5 mL min(-1); channel length: 840 mm), we evaluated the accuracy of the system using a standard addition method; the measured values had agreements of ≥ 93.0% with certified values obtained for Hg(2+) ions. The relative standard deviations of the proposed method ranged from 2.24% to 6.21%. The limit of detection for Hg(2+) for the proposed on-line AuNPs-PDMS/MF/ICP-MS analytical method was as low as 0.07 µg L(-1). Copyright © 2014 Elsevier B.V. All rights reserved.

  7. 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.

  8. Analysis of plutonium isotope ratios including 238Pu/239Pu in individual U-Pu mixed oxide particles by means of a combination of alpha spectrometry and ICP-MS.

    PubMed

    Esaka, Fumitaka; Yasuda, Kenichiro; Suzuki, Daisuke; Miyamoto, Yutaka; Magara, Masaaki

    2017-04-01

    Isotope ratio analysis of individual uranium-plutonium (U-Pu) mixed oxide particles contained within environmental samples taken from nuclear facilities is proving to be increasingly important in the field of nuclear safeguards. However, isobaric interferences, such as 238 U with 238 Pu and 241 Am with 241 Pu, make it difficult to determine plutonium isotope ratios in mass spectrometric measurements. In the present study, the isotope ratios of 238 Pu/ 239 Pu, 240 Pu/ 239 Pu, 241 Pu/ 239 Pu, and 242 Pu/ 239 Pu were measured for individual Pu and U-Pu mixed oxide particles by a combination of alpha spectrometry and inductively coupled plasma mass spectrometry (ICP-MS). As a consequence, we were able to determine the 240 Pu/ 239 Pu, 241 Pu/ 239 Pu, and 242 Pu/ 239 Pu isotope ratios with ICP-MS after particle dissolution and chemical separation of plutonium with UTEVA resins. Furthermore, 238 Pu/ 239 Pu isotope ratios were able to be calculated by using both the 238 Pu/( 239 Pu+ 240 Pu) activity ratios that had been measured through alpha spectrometry and the 240 Pu/ 239 Pu isotope ratios determined through ICP-MS. Therefore, the combined use of alpha spectrometry and ICP-MS is useful in determining plutonium isotope ratios, including 238 Pu/ 239 Pu, in individual U-Pu mixed oxide particles. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Development and application of a method for Cr(III) determination in dairy products by HPLC-ICP-MS.

    PubMed

    Hernandez, Fanny; Jitaru, Petru; Cormant, Florence; Noël, Laurent; Guérin, Thierry

    2018-02-01

    This study describes the development of an analytical approach for the determination of Cr(III) in dairy products by microwave assisted extraction, complexation in situ by ethylenediaminetetraacetate (EDTA) and high performance liquid chromatography hyphenated to inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). The extraction step was optimised by using an experimental design. A limit of quantification of 38µgkg -1 dry weight (d.w.) was obtained whereas the bias (%) measured ranged from 10 to 18%. The repeatability and intermediate precision varied between 1.2-5.0% and 7.5-13.5%, respectively. The method was applied to the analysis of several dairy samples beforehand characterized in terms of Cr(VI) and total chromium (Cr total ). Cr(III) concentrations ranged from <13 to 255µgkg -1 d.w. The results showed a good agreement between Cr(III) and Cr total concentration levels. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Extraction techniques for arsenic species in rice flour and their speciation by HPLC-ICP-MS.

    PubMed

    Narukawa, Tomohiro; Suzuki, Toshihiro; Inagaki, Kazumi; Hioki, Akiharu

    2014-12-01

    The extraction of arsenic (As) species present in rice flour samples was investigated using different extracting solvents, and the concentration of each species was determined by HPLC-ICP-MS after heat-assisted extraction. The extraction efficiencies for total arsenic species and especially for arsenite [As(III)] and arsenate [As(V)] were investigated. As(III), As(V) and dimethylarsinic acid (DMAA) were found in the samples, and the concentration of DMAA did not vary with treatment conditions. However, the concentrations of extracted total arsenic and those of As(III) and As(V) depended on the extracting solvents. When an extracting solvent was highly acidic, the concentrations of extracted total arsenic were in good agreement with the total arsenic concentration determined by ICP-MS after microwave-assisted digestion, though a part of the As(V) was reduced to As(III) during the highly acidic extraction process. Extraction under neutral conditions increased the extracted As(V), but extracted total arsenic was decreased because a part of the As(III) could not be extracted. Optimum conditions for the extraction of As(III) and As(V) from rice flour samples are discussed to allow the accurate determinations of As(III), As(V) and DMAA in the rice flour samples. Heat block extraction techniques using 0.05 mol L(-1) HClO4 and silver-containing 0.15 mol L(-1) HNO3 were also developed. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. 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

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

    USGS Publications Warehouse

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

    2006-01-01

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

  13. A study of method robustness for arsenic speciation in drinking water samples by anion exchange HPLC-ICP-MS.

    PubMed

    Day, Jason A; Montes-Bayón, María; Vonderheide, Anne P; Caruso, Joseph A

    2002-08-01

    Regulating arsenic species in drinking waters is a reasonable objective, since the various species have different toxicological impacts. However, developing robust and sensitive speciation methods is mandatory prior to any such regulations. Numerous arsenic speciation publications exist, but the question of robustness or ruggedness for a regulatory method has not been fully explored. The present work illustrates the use of anion exchange chromatography coupled to ICP-MS with a commercially available "speciation kit" option. The mobile phase containing 2 mM NaH(2)PO(4) and 0.2 mM EDTA at pH 6 allowed adequate separation of four As species (As(III), As(V), MMAA, DMAA) in less than 10 min. The analytical performance characteristics studied, including method detection limits (lower than 100 ng L(-1) for all the species evaluated), proved the suitability of the method to fulfill the current regulation. Other parameters evaluated such as laboratory fortified blanks, spiked recoveries, and reproducibility over a certain period of time produced adequate results. The samples analyzed were taken from water utilities in different areas of the United States and were provided by the U.S. EPA. The data suggests the speciation setup performs to U.S. EPA specifications but sample treatment and chemistry are also important factors for achieving good recoveries for samples spiked with As(III) as arsenite and As(V) as arsenate.

  14. [Study on distribution of five heavy metal elements in different parts of Cordyceps sinensis by microwave digestion ICP-MS].

    PubMed

    Zhou, Li; Hao, Qing-Xiu; Wang, Sheng; Yang, Quan; Kang, Chuan-Zhi; Yang, Wan-Zhen; Guo, Lan-Ping

    2017-08-01

    The contents of five heavy metals (Cu, Pb, As, Cd, Hg) in 17 batches of Cordyceps sinensis were determined by microwave digestion-ICP-MS, and their distribution in C. sinensis were analyzed. The results showed that the contents of Cu, Pb, Cd and Hg in all batches were in accordance with the international standards of Chinese Medicine-Chinese Herbal Medicine Heavy Metal Limit, with their contents in the stroma higher than that in the caterpillar body, and the excess rate of As, which mainly concentrated in the caterpillar body part of C. sinensis, was 88.24%, as the content of As in the caterpillar body was 7 to 12 fold of that in the stroma. In this study, the distribution of five heavy metals in C. sinensis was clarified, and the existing problems of arsenic limit of heavy metal in C. sinensis were analyzed, and some suggestions were put forward. It is hoped that the reference standard can be provided for the limited standard of arsenic in C. sinensis. Copyright© by the Chinese Pharmaceutical Association.

  15. 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.

  16. Determination of lead by hydride generation inductively coupled plasma mass spectrometry (HG-ICP-MS): on-line generation of plumbane using potassium hexacyanomanganate(III)

    PubMed Central

    Yilmaz, Vedat; Arslan, Zikri; Rose, LaKeysha

    2012-01-01

    A hydride generation (HG) procedure has been described for determination of Pb by ICP-MS using potassium hexacyanomanganate(III), K3Mn(CN)6, as an additive to facilitate the generation of plumbane (PbH4). Potassium hexacyanomanganate(III) was prepared in acidic medium as it was unstable in water. The stability of hexacyanomanganate(III) was examined in dilute solutions of HCl, HNO3 and H2SO4. The solutions prepared in 1% v/v/ H2SO4 were found to be stable for over a period of 24 h. The least suitable medium was 1% v/v HNO3. For generation of plumbane, acidic hexacyanomanganate(III) and sample solutions were mixed online along a 5-cm long tygon tubing (1.14 mm i.d.) and then reacted with 2% m/v sodium borohydride (NaBH4). A concentration of 0.5% m/v K3Mn(CN)6 facilitated the generation of PbH4 remarkably. In comparison to H2SO4, HCl provided broader working range for which optimum concentration was 1% v/v. No significant interferences were noted from transition metals and hydride forming elements, up to 0.5 μg mL−1 levels, except Cu which depressed the signals severely. The depressive effects in the presence of 0.1 μg mL−1 Cu were alleviated by increasing the concentration of K3Mn(CN)6 to 2% m/v. Under these conditions, the sensitivity was enhanced by a factor of at least 42 to 48. The detection limit (3s) was 0.008 μg L−1 for 208Pb isotope. Average signal-to-noise ratio (S/N) ranged between 18 and 20 for 1.0 μg mL−1 Pb solution. The accuracy of the method was verified by analysis of several certified reference materials, including Nearshore seawater (CASS-4), Bone ash (SRM 1400), and Mussel tissue (SRM 2976). The procedure was also successfully applied to the determination of Pb in coastal seawater samples by ICP-MS. PMID:23312310

  17. 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

  18. 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.

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

    PubMed

    Nischkauer, Winfried; Vanhaecke, Frank; Limbeck, Andreas

    2016-08-01

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

  20. 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

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

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

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

    2015-01-01

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

  2. In vivo characterization of magnesium alloy biodegradation using electrochemical H2 monitoring, ICP-MS, and XPS.

    PubMed

    Zhao, Daoli; Wang, Tingting; Nahan, Keaton; Guo, Xuefei; Zhang, Zhanping; Dong, Zhongyun; Chen, Shuna; Chou, Da-Tren; Hong, Daeho; Kumta, Prashant N; Heineman, William R

    2017-03-01

    The effect of widely different corrosion rates of Mg alloys on four parameters of interest for in vivo characterization was evaluated: (1) the effectiveness of transdermal H 2 measurements with an electrochemical sensor for noninvasively monitoring biodegradation compared to the standard techniques of in vivo X-ray imaging and weight loss measurement of explanted samples, (2) the chemical compositions of the corrosion layers of the explanted samples by XPS, (3) the effect on animal organs by histology, and (4) the accumulation of corrosion by-products in multiple organs by ICP-MS. The in vivo biodegradation of three magnesium alloys chosen for their widely varying corrosion rates - ZJ41 (fast), WKX41 (intermediate) and AZ31 (slow) - were evaluated in a subcutaneous implant mouse model. Measuring H 2 with an electrochemical H 2 sensor is a simple and effective method to monitor the biodegradation process in vivo by sensing H 2 transdermally above magnesium alloys implanted subcutaneously in mice. The correlation of H 2 levels and biodegradation rate measured by weight loss shows that this non-invasive method is fast, reliable and accurate. Analysis of the insoluble biodegradation products on the explanted alloys by XPS showed all of them to consist primarily of Mg(OH) 2 , MgO, MgCO 3 and Mg 3 (PO 4 ) 2 with ZJ41 also having ZnO. The accumulation of magnesium and zinc were measured in 9 different organs by ICP-MS. Histological and ICP-MS studies reveal that there is no significant accumulation of magnesium in these organs for all three alloys; however, zinc accumulation in intestine, kidney and lung for the faster biodegrading alloy ZJ41 was observed. Although zinc accumulates in these three organs, no toxicity response was observed in the histological study. ICP-MS also shows higher levels of magnesium and zinc in the skull than in the other organs. Biodegradable devices based on magnesium and its alloys are promising because they gradually dissolve and thereby

  3. Correcting sensitivity drift during long-term multi-element signal measurements by solid sampling-ETV-ICP-MS.

    PubMed

    Martin-Esteban, A; Slowikowski, B; Grobecker, K H

    2004-06-17

    Solid sampling-electrothermal vaporisation-inductively coupled plasma-mass spectrometry (SS-ETV-ICP-MS) is an attractive technique for the direct simultaneous determination of trace elements in solid samples and especially in long-term studies (i.e. assessment of the homogeneity of reference materials). However, during these studies a downward drift in the instrument sensitivity has been observed due likely to deposits on the sampling and skimmer cones and on the ion lens of the mass spectrometer. Accordingly, in this paper, several means of correcting and/or suppressing sensitivity drift are proposed and evaluated for the monitoring of Cd, Cu, Hg, Mn, Pb, Sb, Se, Sn, Tl, U and V in different reference materials of inorganic and organic (biological) origin. From that studies, the combination of the use of the argon dimer as internal standard together with a modification in the ETV-ICP connection tube seems to be the best mean of getting stable sensitivity during at least 60 consecutive ETV runs.

  4. The limitations on organic detection in Mars-like soils by thermal volatilization–gas chromatography–MS and their implications for the Viking results

    PubMed Central

    Navarro-González, Rafael; Navarro, Karina F.; de la Rosa, José; Iñiguez, Enrique; Molina, Paola; Miranda, Luis D.; Morales, Pedro; Cienfuegos, Edith; Coll, Patrice; Raulin, François; Amils, Ricardo; McKay, Christopher P.

    2006-01-01

    The failure of Viking Lander thermal volatilization (TV) (without or with thermal degradation)–gas chromatography (GC)–MS experiments to detect organics suggests chemical rather than biological interpretations for the reactivity of the martian soil. Here, we report that TV–GC–MS may be blind to low levels of organics on Mars. A comparison between TV–GC–MS and total organics has been conducted for a variety of Mars analog soils. In the Antarctic Dry Valleys and the Atacama and Libyan Deserts we find 10–90 μg of refractory or graphitic carbon per gram of soil, which would have been undetectable by the Viking TV–GC–MS. In iron-containing soils (jarosites from Rio Tinto and Panoche Valley) and the Mars simulant (palogonite), oxidation of the organic material to carbon dioxide (CO2) by iron oxides and/or their salts drastically attenuates the detection of organics. The release of 50–700 ppm of CO2 by TV–GC–MS in the Viking analysis may indicate that an oxidation of organic material took place. Therefore, the martian surface could have several orders of magnitude more organics than the stated Viking detection limit. Because of the simplicity of sample handling, TV–GC–MS is still considered the standard method for organic detection on future Mars missions. We suggest that the design of future organic instruments for Mars should include other methods to be able to detect extinct and/or extant life. PMID:17060639

  5. The limitations on organic detection in Mars-like soils by thermal volatilization-gas chromatography-MS and their implications for the Viking results.

    PubMed

    Navarro-González, Rafael; Navarro, Karina F; de la Rosa, José; Iñiguez, Enrique; Molina, Paola; Miranda, Luis D; Morales, Pedro; Cienfuegos, Edith; Coll, Patrice; Raulin, François; Amils, Ricardo; McKay, Christopher P

    2006-10-31

    The failure of Viking Lander thermal volatilization (TV) (without or with thermal degradation)-gas chromatography (GC)-MS experiments to detect organics suggests chemical rather than biological interpretations for the reactivity of the martian soil. Here, we report that TV-GC-MS may be blind to low levels of organics on Mars. A comparison between TV-GC-MS and total organics has been conducted for a variety of Mars analog soils. In the Antarctic Dry Valleys and the Atacama and Libyan Deserts we find 10-90 mug of refractory or graphitic carbon per gram of soil, which would have been undetectable by the Viking TV-GC-MS. In iron-containing soils (jarosites from Rio Tinto and Panoche Valley) and the Mars simulant (palogonite), oxidation of the organic material to carbon dioxide (CO(2)) by iron oxides and/or their salts drastically attenuates the detection of organics. The release of 50-700 ppm of CO(2) by TV-GC-MS in the Viking analysis may indicate that an oxidation of organic material took place. Therefore, the martian surface could have several orders of magnitude more organics than the stated Viking detection limit. Because of the simplicity of sample handling, TV-GC-MS is still considered the standard method for organic detection on future Mars missions. We suggest that the design of future organic instruments for Mars should include other methods to be able to detect extinct and/or extant life.

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2006-03-01

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

  8. Resolving global versus local/regional Pu sources in the environment using sector ICP-MS

    USGS Publications Warehouse

    Ketterer, M.E.; Hafer, K.M.; Link, C.L.; Kolwaite, D.; Wilson, Jim; Mietelski, J.W.

    2004-01-01

    Sector inductively coupled plasma mass spectrometry is a versatile method for the determination of plutonium activities and isotopic compositions in samples containing this element at fallout levels. Typical detection limits for 239+240Pu are 0.1, 0.02 and 0.002 Bq kg -1Pu for samples sizes of 0.5 g, 3 g, and 50 g of soil, respectively. The application of sector ICP-MS-based Pu determinations is demonstrated in studies in sediment chronology, soil Pu inventory and depth distribution, and the provenance of global fallout versus local or regional Pu sources. A sediment core collected from Sloans Lake (Denver, Colorado, USA) exhibits very similar 137Cs and 239+240Pu activity profiles; 240Pu/239Pu atom ratios indicate possible small influences from the Nevada Test Site and/or the Rocky Flats Environmental Technology Site. An undisturbed soil profile from Lockett Meadow (Flagstaff, Arizona, USA) exhibits an exponential decrease in 239+240Pu activity versus depth; 240Pu/239Pu in the top 3 cm is slightly lower than the global fallout range of 0.180 ?? 0.014 due to possible regional influence of Nevada Test Site fallout. The 239??240Pu inventory at Lockett Meadow is 56 ?? 4 Bq m-2, consistent with Northern Hemisphere mid-latitude fallout. Archived NdF3 sources, prepared from Polish soils, demonstrate that substantial 239+240Pu from the 1986 Chernobyl disaster has been deposited in north eastern regions of Poland; compared to global fallout, Chernobyl Pu exhibits higher abundances of 240Pu and 241Pu. The ratios 240Pu/239pu and 241Pu/239Pu co-vary and range from 0.186-0.348 and 0.0029-0.0412, respectively, in forest soils (241Pu/239Pu = 0.2407??[240Pu/239Pu] - 0.0413; r2 = 0.9924). ?? The Royal Society of Chemistry 2004.

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

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

    Di Vacri, M. L., E-mail: divacrim@lngs.infn.it; Dipartimento di Scienze Fisiche e Chimiche, University of L’Aquila, via Vetoio, 67100 L’Aquila; Nisi, S., E-mail: nisi@lngs.infn.it

    2015-08-17

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    below the detection limit of LA-ICP-MS (~30 ppb). However, these trace elements change the cathodoluminescence properties of ZnS. The concentration or gold in covellite was determined by both LA-ICP-MS and EPMA techniques and the final values clearly fit together. The maximum concentration can be observed at 450° and equal to 0.3wt%. This value changes minor due to the increasing of the temperature. In principle, adding admixtures of In, Zn, Se, Cu, Sb, Bi did not affect on the concentration of Au. However, in experiment where sulfur is excessive and a mixture of In, Zn, Se, Cu, Sb, Bi, were added the concentration of Au is equal 0.128+0.028 ppm. The gold distribution in covellite and sphalerite is always homogeneous. According to XANES data, atoms of Au in the crystal structure covellite is in triangles, formed by the atoms of Cu. In sphalerite gold is in "invisible" state too.

  11. 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.

  12. Microfluidic LC Device with Orthogonal Sample Extraction for On-Chip MALDI-MS Detection

    PubMed Central

    Lazar, Iulia M.; Kabulski, Jarod L.

    2013-01-01

    A microfluidic device that enables on-chip matrix assisted laser desorption ionization-mass spectrometry (MALDI-MS) detection for liquid chromatography (LC) separations is described. The device comprises an array of functional elements to carry out LC separations, integrates a novel microchip-MS interface to facilitate the orthogonal transposition of the microfluidic LC channel into an array of reservoirs, and enables sensitive MALDI-MS detection directly from the chip. Essentially, the device provides a snapshot MALDI-MS map of the content of the separation channel present on the chip. The detection of proteins with biomarker potential from MCF10A breast epithelial cell extracts, and detection limits in the low fmol range, are demonstrated. In addition, the design of the novel LC-MALDI-MS chip entices the promotion of a new concept for performing sample separations within the limited time-frame that accompanies the dead-volume of a separation channel. PMID:23592150

  13. Platinum concentration in silicone breast implant material and capsular tissue by ICP-MS.

    PubMed

    Maharaj, S V M

    2004-09-01

    Inductively coupled plasma-mass spectrometry (ICP-MS) was used to determine the concentration of platinum (Pt) in silicone breast implant gel (range, 0.26-48.90 microg g(-1) Pt; n=15), elastomer (range, 3.05-28.78 microg g(-1) Pt; n=7), double lumen (range, 5.79-125.27 microg g(-1) Pt; n=7), foam (range, 5.79-8.36 microg g(-1) Pt; n=2), and capsular tissue (range, 0.003-0.272 microg g(-1) Pt; n=15). The results show that very high levels of Pt are present in the encasing elastomer, double lumen, and foam envelope materials. Silicone breast implants can be a source of significant Pt exposure for individuals with these implants.

  14. High resolution ID-ICP-MS certification of an estuary water reference material (LGC 6016) and analysis of matrix induced polyatomic interferences.

    PubMed

    Evans, P; Fairman, B

    2001-10-01

    Reliable trace metal analysis of environmental samples is dependent upon the availability of high accuracy, matrix reference standards. Here, we present Cd, Cu, Ni, Pb and Zn isotope dilution determination for an estuary water certified reference material (LGC 6016). This work highlights the need for high-accuracy techniques in the development of trace element CRMs rather than conventional inter-laboratory trials. Certification of the estuary water LGC6016 was initially determined from a consensus mean from 14 laboratories but this was found to be unsatisfactory due to the large discrepancies in the reported concentrations. The material was re-analysed using isotope dilution ICP-MS techniques. Pb and Cd were determined using a conventional quadrupole ICP-MS (Elan 5000). Cu, Zn and Ni were determined using a magnetic sector ICP-MS (Finnigan Element), which allowed significant polyatomic interferences to be overcome. Using the magnetic sector instrument, precise mass calibration to within 0.02 amu permitted identification of the interferences. Most interferences derived from the sample matrix. For example, the high Na content causes interferences on 63Cu, due to the formation of 40Ar23Na and 23Na2 16O1H, which in a conventional quadrupole instrument would relate to an erroneous increase in signal intensity by up to 20%. For each analyte a combined uncertainty calculation was performed following the Eurachem/GTAC and ISO guideline. For each element a combined uncertainty of 2-3% was found, which represents a 10-fold improvement compared to certification by inter-laboratory comparison. Analysis of the combined uncertainty budget indicates that the majority of systematic uncertainty derives from the instrumental isotope ratio measurements.

  15. [Study on arsenic speciation changes in crude and processed traditional Chinese medicines by HPLC-ICP-MS].

    PubMed

    Jin, Peng-fei; Wu, Xue-jun; Zou, Ding; Kuang, Yong-mei; Hu, Xin; Jiang, Wen-qing; Sun, Chun-hua

    2011-03-01

    A HPLC-ICP-MS method for simultaneous determination of As(III), As(V), MMA and DMA in traditional Chinese medicines (TCMs) was established, and the contents of As(III), As(V), MMA and DMA in a TCM with high total arsenic content (Cordyceps) and 5 crude and processed TCMs (Radix Astragali, Radix et Rhizoma Rhei, Radix Scutellariae, Radix Polygoni Multiflori and Radix Rehmanniae) were determined and analyzed. The method validation indicated that the correlative coefficients (r) for all speciations were bigger than 0.9984; the limits of quantitation (LOQ) were from 0.8 to 1.0 microg x L(-1); the reproducibility and stability were satisfactory with all RSDs less than 10%; the spiked recoveries ranged from 82.40% to 119.5%. The results of samples analysis showed that the inorganic arsenic (As(III) and As(V)) was the dominating speciation in the tested TCMs; MMA and DMA were not found in all plant resourced TCMs, but MMA was found in Cordyceps; all the tested TCMs indicated a content increasing of inorganic arsenic after processing.

  16. Toxic metal levels in cocoa powder and chocolate by ICP-MS method after microwave-assisted digestion.

    PubMed

    Lo Dico, Gianluigi Maria; Galvano, Fabio; Dugo, Giacomo; D'ascenzi, Carlo; Macaluso, Andrea; Vella, Antonio; Giangrosso, Giuseppe; Cammilleri, Gaetano; Ferrantelli, Vincenzo

    2018-04-15

    The Commission Regulation (EC) Regulation N. 488/2014, established the concentration limits for cadmium in specific products based on cocoa and chocolate products as from January 2019. Based on this information there is a need to determine ultratrace levels of elements that might be presents in cocoa and chocolate products. In this work, the concentrations of Arsenic, Antimony, Cadmium, Chromium, Lead, Selenium and Vanadium were evaluated in cocoa powder and chocolate by the validation of an ICP-MS method. Good selectivity/specificity, recovery, repeatability and within-laboratory reproducibility, LOD, LOQ, range of linearity, standard measurement uncertainty parameters for method validation were achieved, in accordance with Commission Regulation. The cocoa powder revealed the maximum metal concentrations of 0.303 ± 0.035 mg/kg for cadmium, 1.228 ± 0.146 mg/kg for lead and 0.094 ± 0.013 mg/kg for arsenic. A significant difference was found between cocoa powder and chocolate samples (p < .05). Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Determination of Arsenic Species in Ophiocordyceps sinensis from Major Habitats in China by HPLC-ICP-MS and the Edible Hazard Assessment.

    PubMed

    Guo, Lian-Xian; Zhang, Gui-Wei; Wang, Jia-Ting; Zhong, Yue-Ping; Huang, Zhi-Gang

    2018-04-26

    This study sought to determine the concentration and distribution of arsenic (As) species in Ophiocordyceps sinensis ( O. sinensis ), and to assess its edible hazard for long term consumption. The total arsenic concentrations, measured through inductively coupled plasma mass spectrometry (ICP-MS), ranged from 4.00 mg/kg to 5.25 mg/kg. As determined by HPLC-ICP-MS, the most concerning arsenic species—AsB, MMA V , DMA V , As V , and As Ш —were either not detected (MMA V and DMA V ) or were detected as minor As species (AsB: 1.4⁻2.9%; As V : 1.3⁻3.2%, and As Ш : 4.1⁻6.0%). The major components were a cluster of unknown organic As (uAs) compounds with As Ш , which accounted for 91.7⁻94.0% of the As content. Based on the H₂O₂ test and the chromatography behavior, it can be inferred that, the uAs might not be toxic organic As. Estimated daily intake ( EDI) , hazard quotient ( HQ ), and cancer risk ( CR ) caused by the total As content; the sum of inorganic As (iAs) and uAs, namely i+uAs; and iAs exposure from long term O. sinensis consumption were calculated and evaluated through equations from the US Environmental Protection Agency and the uncertainties were analyzed by Monte-Carlo Simulation (MCS). EDI total As and EDI i+uAs are approximately ten times more than EDI iAs ; HQ total As and HQ i+u As > 1 while HQ i As < 1; and CR total As and CR i+uAs > 1 × 10 −4 while CR iAs < 1 × 10 −4 . Thus, if the uAs is non-toxic, there is no particular risk to local consumers and the carcinogenic risk is acceptable for consumption of O. sinensis because the concentration of toxic iAs is very low.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  19. 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.

  20. Measuring the content of 17 elements in the flesh of Prunus cerasifera and its cultivars by ICP-MS.

    PubMed

    Shen, Jing; Xue, Hai-Yan; Li, Gai-Ru; Lu, Yi; Yao, Jun

    2014-09-01

    The present study compared the contents of inorganic elements in the pulp of purple, red, and yellow Prunus cerasifera with its cultivars. A method was established for the analysis of 17 kinds of trace elements (K, Ca, Mg, Na, Fe, Mn, Cu, Zn, Be, Li, Se, Sr, Cr, Pb, Cd, As and Hg) in the flesh of Prunus cerasifera by microwave digestion-ICP-MS. The detection method is simple and quick, yet shoes high precision and high sensitivity. The recovery rate of 17 elements ranged, from 93.5% to 110.4%. The analysis results showed that the contents of 17 elements in the flesh of purple, red, and yellow Prunus cerasifera and its cultivars are similar, containing extremely rich K elements (as high as 1 per thousand) and higher contents of Ca, Mg, Na, Fe and Mn. The contents of Cu, Zn, Li, Se, Sr and Cr are also present. The contents of Pb, Cd, As, Hg and other harmful element are either very low or not detectable. The experimental results for the study of trace elements in pulp of Prunus cerasifera and its cultivars provide empirical data for. future research in this area.

  1. 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.

  2. 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

  3. New approach of a transient ICP-MS measurement method for samples with high salinity.

    PubMed

    Hein, Christina; Sander, Jonas Michael; Kautenburger, Ralf

    2017-03-01

    In the near future it is necessary to establish a disposal for high level nuclear waste (HLW) in deep and stable geological formations. In Germany typical host rocks are salt or claystone. Suitable clay formations exist in the south and in the north of Germany. The geochemical conditions of these clay formations show a strong difference. In the northern ionic strengths of the pore water up to 5M are observed. The determination of parameters like K d values during sorption experiments of metal ions like uranium or europium as homologues for trivalent actinides onto clay stones are very important for long term safety analysis. The measurement of the low concentrated, not sorbed analytes commonly takes place by inductively coupled plasma mass spectrometry (ICP-MS). A direct measurement of high saline samples like seawater with more than 1% total dissolved salt content is not possible. Alternatives like sample clean up, preconcentration or strong dilution have more disadvantages than advantages for example more preparation steps or additional and expensive components. With a small modification of the ICP-MS sample introduction system and a home-made reprogramming of the autosampler a transient analysing method was developed which is suitable for measuring metal ions like europium and uranium in high saline sample matrices up to 5M (NaCl). Comparisons at low ionic strength between the default and the transient measurement show the latter performs similarly well to the default measurement. Additionally no time consuming sample clean-up or expensive online dilution or matrix removal systems are necessary and the analysation shows a high sensitivity due to the data processing based on the peak area. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. 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.

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

    PubMed

    Wojcieszek, Justyna; Ruzik, Lena

    2016-03-01

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

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

    PubMed Central

    Suhr, Matthias; Raff, Johannes; Pollmann, Katrin

    2016-01-01

    In this publication the gold sorption behavior of surface layer (S-layer) proteins (Slp1) of Lysinibacillus sphaericus JG-B53 is described. These biomolecules arrange in paracrystalline two-dimensional arrays on surfaces, bind metals, and are thus interesting for several biotechnical applications, such as biosorptive materials for the removal or recovery of different elements from the environment and industrial processes. The deposition of Au(0) nanoparticles on S-layers, either by S-layer directed synthesis 1 or adsorption of nanoparticles, opens new possibilities for diverse sensory applications. Although numerous studies have described the biosorptive properties of S-layers 2-5, a deeper understanding of protein-protein and protein-metal interaction still remains challenging. In the following study, inductively coupled mass spectrometry (ICP-MS) was used for the detection of metal sorption by suspended S-layers. This was correlated to measurements of quartz crystal microbalance with dissipation monitoring (QCM-D), which allows the online detection of proteinaceous monolayer formation and metal deposition, and thus, a more detailed understanding on metal binding. The ICP-MS results indicated that the binding of Au(III) to the suspended S-layer polymers is pH dependent. The maximum binding of Au(III) was obtained at pH 4.0. The QCM-D investigations enabled the detection of Au(III) sorption as well as the deposition of Au(0)-NPs in real-time during the in situ experiments. Further, this method allowed studying the influence of metal binding on the protein lattice stability of Slp1. Structural properties and protein layer stability could be visualized directly after QCM-D experiment using atomic force microscopy (AFM). In conclusion, the combination of these different methods provides a deeper understanding of metal binding by bacterial S-layer proteins in suspension or as monolayers on either bacterial cells or recrystallized surfaces. PMID:26863150

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

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

    Kubachka, Kevin M.; Kohan, Michael C.; Herbin-Davis, Karen

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

  8. 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

  9. Isotope dilution inductively coupled plasma mass spectrometry (ID ICP-MS) for the certification of lead and cadmium in environmental standard reference materials.

    PubMed

    Murphy, K E; Beary, E S; Rearick, M S; Vocke, R D

    2000-10-01

    Lead (Pb) and cadmium (Cd) have been determined in six new environmental standard reference materials (SRMs) using isotope dilution inductively coupled plasma mass spectrometry (ID ICP-MS). The SRMs are the following: SRM 1944, New York-New Jersey Waterway Sediment, SRMs 2583 and 2584, Trace Elements in Indoor Dust, Nominal 90 mg/kg and 10,000 mg/kg Lead, respectively, SRMs 2586 and 2587, Trace Elements in Soil Containing Lead from Paint, Nominal 500 mg/kg and 3,000 mg/kg Lead, respectively, and SRM 2782, Industrial Sludge. The capabilities of ID ICP-MS for the certification of Pb and Cd in these materials are assessed. Sample preparation and ratio measurement uncertainties have been evaluated. Reproducibility and accuracy of the established procedures are demonstrated by determination of gravimetrically prepared primary standard solutions and by comparison with isotope dilution thermal ionization mass spectrometry (ID TIMS). Material heterogeneity was readily demonstrated to be the dominant source of uncertainty in the certified values.

  10. 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.

  11. 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.

  12. Determination of alkyllead compounds by HPLC/ICP using a glass-frit nebulizer ICP interface

    NASA Astrophysics Data System (ADS)

    Ibrahim, Mona; Nisamaneepong, Wipawan; Haas, David L.; Caruso, Joseph A.

    The glass-frit nebulizer, by forming a very fine mist, has improved the ability of the ICP to accept the introduction of organic solvents with high evaporation rates. The reversed-phase chromatographic separation of TML and TEL, and their determination with glass frit nebulization ICP was accomplished with various mobile phases and columns. The separation of several trialkyllead salts also was studied on a strong cation exchange column, but these compounds were not determined with the glass frit nebulizer interface. Detection limits as low as 33 pg s -1 for TML and 100 pg s -1 for TEL and precision of 3.4% for TML and 6.9% relative standard deviation for TEL were obtained.

  13. Profiling extractable and leachable inorganic impurities in ophthalmic drug containers by ICP-MS.

    PubMed

    Solomon, Paige; Nelson, Jenny

    2018-03-01

    In this study, we investigated the elemental impurities present in the plastic material of ophthalmic eye drop bottles using inductively coupled plasma-mass spectrometry (ICP-MS). Metallic contaminations, especially localized within the small cavity of the eye, can significantly perturb the ocular metallome. The concern is two-fold: first certain elements, for example heavy metals, can be toxic to humans at even trace levels, and second, these contaminations can have adverse reactions with other medicines or enzymatic processes in the eye. The implication of redox-active metals in cataract formation is one such biological consequence. The analysis demonstrated the effect of aggressive storage and transportation conditions on elemental extractable and leachable contamination, and posits that release of these elemental impurities can disrupt metallome equilibrium in the ocular compartment, leading to toxicity and disease.

  14. 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.

  15. 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.

  16. Tissue gadolinium deposition in hepatorenally impaired rats exposed to Gd-EOB-DTPA: evaluation with inductively coupled plasma mass spectrometry (ICP-MS).

    PubMed

    Sato, Tomohiro; Tamada, Tsutomu; Watanabe, Shigeru; Nishimura, Hirotake; Kanki, Akihiko; Noda, Yasufumi; Higaki, Atsushi; Yamamoto, Akira; Ito, Katsuyoshi

    2015-06-01

    This study was undertaken to quantify tissue gadolinium (Gd) deposition in hepatorenally impaired rats exposed to gadolinium ethoxybenzyl diethylenetriamine pentaacetic acid (Gd-EOB-DTPA) by means of inductively coupled plasma mass spectrometry (ICP-MS) and to compare differences in Gd distribution among major organs as possible triggers for nephrogenic systemic fibrosis. Five hepatorenally impaired rats (5/6-nephrectomized, with carbon-tetrachloride-induced liver fibrosis) were injected with Gd-EOB-DTPA. Histological assessment was conducted and Gd content of the skin, liver, kidneys, lungs, heart, spleen, diaphragm, and femoral muscle was measured by inductively coupled plasma mass spectrometry (ICP-MS) at 7 days after last injection. In addition, five renally impaired rats were injected with Gd-EOB-DTPA and the degree of tissue Gd deposition was compared with that in the hepatorenally impaired rats. ICP-MS analysis revealed significantly higher Gd deposition in the kidneys, spleen, and liver (p = 0.009-0.047) in the hepatorenally impaired group (42.6 ± 20.1, 17.2 ± 6.1, 8.4 ± 3.2 μg/g, respectively) than in the renally impaired group (17.2 ± 7.7, 5.4 ± 2.1, 2.8 ± 0.7 μg/g, respectively); no significant difference was found for other organs. In the hepatorenally impaired group, Gd was predominantly deposited in the kidneys, followed by the spleen, liver, lungs, skin, heart, diaphragm, and femoral muscle. Histopathological investigation revealed hepatic fibrosis in the hepatorenally impaired group. Compared with renally impaired rats, tissue Gd deposition in hepatorenally impaired rats exposed to Gd-EOB-DTPA was significantly increased in the kidneys, spleen, and liver, probably due to the impairment of the dual excretion pathways of the urinary and biliary systems.

  17. 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

  18. Detection of the Spermicide Nonoxynol-9 Via GC-MS

    NASA Astrophysics Data System (ADS)

    Musah, Rabi A.; Vuong, Angela L.; Henck, Colin; Shepard, Jason R. E.

    2012-05-01

    The spermicide nonoxynol-9 is actually a complex mixture of dozens of closely related amphiphilic compounds, and the chemical properties of this assortment significantly hamper its characterization by GC-MS. The inability to perform routine GC-MS testing on nonoxynol-9 has limited its evidentiary value in forensic casework, which relies heavily on this technique for analysis. A disturbing trend in sexual assault is the use of condoms by assailants, to avoid leaving behind DNA evidence that can connect a perpetrator to a victim. This observation necessitates the development of alternative methods for the analysis of trace evidence that can show causal links between a victim and a suspect. Detection of lubricants associated with sexual assault is one such way to establish this connection. The development of GC-MS methods that permit facile detection of both nonoxynol-9 alone and nonoxynol-9 extracted from other complex matrices that have potential as trace evidence in sexual assault is reported. A detection limit of 2.14 μg of nonoxynol-9 is demonstrated, and a detailed mass spectral profile that elaborates on what is known of its structure is provided.

  19. 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.

  20. Combination of ICP-MS, capillary electrophoresis, and their hyphenation for probing Ru(III) metallodrug-DNA interactions.

    PubMed

    Foteeva, Lidia S; Matczuk, Magdalena; Pawlak, Katarzyna; Aleksenko, Svetlana S; Nosenko, Sergey V; Karandashev, Vasily K; Jarosz, Maciej; Timerbaev, Andrei R

    2017-03-01

    Determination of the DNA-binding reactivity and affinity is an important part of a successful program for the selection of metallodrug candidates. For such assaying, a range of complementary analytical techniques was proposed and tested here using one of few anticancer metal-based drugs that are currently in clinical trials, indazolium trans-[tetrachloridobis(1H-indazole)ruthenate(III), and a DNA oligonucleotide. A high reactivity of the Ru drug was confirmed in affinity capillary electrophoresis (CE) mode, where adduct formation takes place in situ (i.e., in the capillary filled with an oligonucleotide-containing electrolyte). To further characterize the binding kinetics, a drug-oligonucleotide mixture was incubated for a different period of time, followed by ultrafiltration separation into two different in molecular weight fractions (>3 and <3 kDa). The time-dependent distribution profiles of the Ru drug were then assessed by CE-inductively coupled plasma mass spectrometry (ICP-MS), revealing that at least two DNA adducts exist at equilibrium conditions. Using standalone ICP-MS, dominant equilibrium amount of the bound ruthenium was found to occur in a fraction of 5-10 kDa, which includes the oligonucleotide (ca. 6 kDa). Importantly, in all three assays, the drug was used for the first time in in-vitro studies, not in the intact form but as its active species released from the transferrin adduct at simulated cancer cytosolic conditions. This circumstance makes the established analytical platform promising to provide a detailed view on metallodrug targeting, including other possible biomolecules and ex vivo samples.

  1. 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

  2. Comparison of TIMS and MC-ICP-MS Analyses of Pb Isotopic Compositions on Prehistoric Mauna Loa Basalts: Implications for Plume Source Components

    NASA Astrophysics Data System (ADS)

    De Jong, J.; Weis, D.; Maerschalk, C.; Rhodes, J. M.

    2001-12-01

    Recent isotopic studies on Hawaiian lavas have shown the necessity of constraining fractionation for Pb isotopes. This isotopic system presents systematic variations reflecting the presence of different plume components in the source of Hawaiian basalts. We have analyzed a series of 23 tholeiitic Mauna Loa basalts ranging in age from 36,780 to 140 y for their Pb isotopic compositions by TIMS (Micromass Sector 54) and MC-ICP-MS (Nu Plasma) to directly compare results from the same, carefully leached, samples. These analyses indicate an internal precision better than 120 ppm for the MC-ICP-MS Pb ratios, while for the TIMS ratios, it is in the per mil range. This results in a more coherent dataset for the MC-ICP-MS analyses, with the range of 207Pb/204Pb variations decreasing by a factor of 3 and of 208Pb/204Pb ratios by a factor of 1.5. The co-variations between the Pb isotopic data and other geochemical parameters for the Hawaiian lavas are now much stronger and better defined. There are clearly two groups amongst the prehistoric Mauna Loa basalts: one group with higher 87Sr/86Sr (>0.7038) and low 206Pb/204Pb (<18.15) that covers the entire range of Nb/Y (0.31 to 0.51) observed in this volcano, and the other group with low 87Sr/86Sr (<0.7038) and higher 206Pb/204Pb with Nb/Y<0.4. The second group is only present in basalts younger than 3,000 y or older than 24,000 y. The high 87Sr/86Sr group was not sampled in the HSDP I drill core, which covers an age range of 100,000 y. This either reflects a sampling bias, as the upper flow units (<10,000 y) were not sampled for geochemistry, or variations in magma supply. Altogether, Mauna Loa lava flows that are younger than 20,000 y show much more isotopic variation than older flows and there is a nearly continuous transition away from the Kilauea component. This may indicate that the transition between the Mauna Loa and Mauna Kea trends is not as sharp as previously documented. This study shows the importance of reducing the

  3. 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.

  4. 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.

  5. The impact of whole human blood on the kinetic inertness of platinum(iv) prodrugs - an HPLC-ICP-MS study.

    PubMed

    Theiner, Sarah; Grabarics, Márkó; Galvez, Luis; Varbanov, Hristo P; Sommerfeld, Nadine S; Galanski, Markus; Keppler, Bernhard K; Koellensperger, Gunda

    2018-04-17

    The potential advantage of platinum(iv) complexes as alternatives to classical platinum(ii)-based drugs relies on their kinetic stability in the body before reaching the tumor site and on their activation by reduction inside cancer cells. In this study, an analytical workflow has been developed to investigate the reductive biotransformation and kinetic inertness of platinum(iv) prodrugs comprising different ligand coordination spheres (respectively, lipophilicity and redox behavior) in whole human blood. The distribution of platinum(iv) complexes in blood pellets and plasma was determined by inductively coupled plasma-mass spectrometry (ICP-MS) after microwave digestion. An analytical approach based on reversed-phase (RP)-ICP-MS was used to monitor the parent compound and the formation of metabolites using two different extraction procedures. The ligand coordination sphere of the platinum(iv) complexes had a significant impact on their accumulation in red blood cells and on their degree of kinetic inertness in whole human blood. The most lipophilic platinum(iv) compound featuring equatorial chlorido ligands showed a pronounced penetration into blood cells and a rapid reductive biotransformation. In contrast, the more hydrophilic platinum(iv) complexes with a carboplatin- and oxaliplatin-core exerted kinetic inertness on a pharmacologically relevant time scale with notable amounts of the compound accumulated in the plasma fraction.

  6. Quantification issues of trace metal contaminants on silicon wafers by means of TOF-SIMS, ICP-MS, and TXRF

    NASA Astrophysics Data System (ADS)

    Rostam-Khani, P.; Hopstaken, M. J. P.; Vullings, P.; Noij, G.; O'Halloran, O.; Claassen, W.

    2004-06-01

    Measurement of surface metal contamination on silicon wafers is essential for yield enhancement in IC manufacturing. Vapor phase decomposition coupled with either inductively coupled plasma mass spectrometry (VPD-ICP-MS), or total reflection X-ray fluorescence (VPD-TXRF), TXRF and more recently time of flight secondary ion mass spectrometry (TOF-SIMS) are used to monitor surface metal contamination. These techniques complement each other in their respective strengths and weaknesses. For reliable and accurate quantification, so-called relative sensitivity factors (RSF) are required for TOF-SIMS analysis. For quantification purposes in VPD, the collection efficiency (CE) is important to ensure complete collection of contamination. A standard procedure has been developed that combines the determination of these RSFs as well as the collection efficiency using all the analytical techniques mentioned above. Therefore, sample wafers were intentionally contaminated and analyzed (by TOF-SIMS) directly after preparation. After VPD-ICP-MS, several scanned surfaces were analyzed again by TOF-SIMS. Comparing the intensities of the specific metals before and after the VPD-DC procedure on the scanned surface allows the determination of so-called removing efficiency (RE). In general, very good agreement was obtained comparing the four analytical techniques after updating the RSFs for TOF-SIMS. Progress has been achieved concerning the CE evaluation as well as determining the RSFs more precisely for TOF-SIMS.

  7. Use of TEVA resin for the determination of U isotopes in water samples by Q-ICP-MS.

    PubMed

    Tagami, K; Uchida, S

    2004-01-01

    In order to measure uranium isotopic mass ratio in natural water samples by Q-ICP-MS, an application of TEVA resin (Eichrom) was studied to separate and concentrate U. After being evaporated to dryness, the sample residue was dissolved in 6 M HCl, then, TEVA extraction was carried out. U extracted on the resin could be removed with 20 ml of 1 M HCl (U fraction) when Fe content was lower than 2 mg. U recovery in U fraction showed a negative correlation with Fe content in the samples.

  8. Ionic liquids improved reversed-phase HPLC on-line coupled with ICP-MS for selenium speciation.

    PubMed

    Chen, Beibei; He, Man; Mao, Xiangju; Cui, Ran; Pang, Daiwen; Hu, Bin

    2011-01-15

    Room-temperature ionic liquids (RTILs) improved reversed-phase high performance liquid chromatography (RP-HPLC) on-line combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for selenium speciation. The different parameters affecting the retention behaviors of six target selenium species especially the effect of RTILs as mobile phase additives have been studied, it was found that the mobile phase consisting of 0.4% (v/v) 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), 0.4% (v/v) 1-butyl-2,3-dimethylimidazolium tetrafluroborate ([BMMIM]BF(4)) and 99.2% (v/v) water has effectively improved the peak profile and six target selenium species including Na(2)SeO(3) (Se(IV)), Na(2)SeO(4) (Se(VI)), L-selenocystine (SeCys(2)), D,L-selenomethionine (SeMet), Se-methylseleno-l-cysteine (MeSeCys), seleno-D,L-ethionine (SeEt) were separated in 8 min. In order to validate the accuracy of the method, a Certified Reference Material of SELM-1 yeast sample was analyzed and the results obtained were in good agreement with the certified values. The developed method was also successfully applied to the speciation of selenium in Se-enriched yeasts and clover. For fresh Se-enriched yeast cells, it was found that the spiked SeCys(2) in living yeast cells could be transformed into SeMet. Compared with other ion-pair RP-HPLC-ICP-MS approaches for selenium speciation, the proposed method possessed the advantages including ability to regulate the retention time of the target selenium species by selecting the suitable RTILs and their concentration, simplicity, rapidness and low injection volume, thus providing wide potential applications for elemental speciation in biological systems. Copyright © 2010 Elsevier B.V. All rights reserved.

  9. HPLC-ICP-MS speciation analysis of arsenic in urine of Japanese subjects without occupational exposure.

    PubMed

    Hata, Akihisa; Endo, Yoko; Nakajima, Yoshiaki; Ikebe, Maiko; Ogawa, Masanori; Fujitani, Noboru; Endo, Ginji

    2007-05-01

    The toxicity and carcinogenicity of arsenic depend on its species. Individuals living in Japan consume much seafood that contains high levels of organoarsenics. Speciation analysis of urinary arsenic is required to clarify the health risks of arsenic intake. There has been no report of urinary arsenic analysis in Japan using high performance liquid chromatography with inductively coupled plasma mass spectrometry (HPLC-ICP-MS). We performed speciation analysis of urinary arsenic for 210 Japanese male subjects without occupational exposure using HPLC-ICP-MS. The median values of urinary arsenics were as follows: sodium arsenite (AsIII), 3.5; sodium arsenate (AsV), 0.1; monomethylarsonic acid (MMA), 3.1; dimethylarsinic acid (DMA), 42.6; arsenobetaine (AsBe), 61.3; arsenocholine, trimethylarsine oxide, and unidentified arsenics (others), 5.2; and total arsenic (total As), 141.3 microgAs/l. The median creatinine-adjusted values were as follows: AsIII, 3.0; AsV, 0.1; MMA, 2.6; DMA, 35.9; AsBe, 52.1; others 3.5; and total As, 114.9 microgAs/g creatinine. Our findings indicate that DMA and AsBe levels in Japan are much higher than those found in Italian and American studies. It appears that the high levels of DMA and AsBe observed in Japan may be due in part to seafood intake. ACGIH and DFG set the BEI and BAT values for occupational arsenic exposure as 35 microgAs/l and 50 microgAs/l, respectively, using the sum of inorganic arsenic (iAs), MMA, and DMA. In the general Japanese population, the sums of these were above 50 microgAs/l in 115 (55%) samples. We therefore recommend excluding DMA concentration in monitoring of iAs exposure.

  10. Determination of Heavy Metals in Almonds and Mistletoe as a Parasite Growing on the Almond Tree Using ICP-OES or ICP-MS.

    PubMed

    Kamar, Veysi; Dağalp, Rukiye; Taştekin, Mustafa

    2017-12-28

    In this study, the elements of Al, As, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Ni, Sr, Pb, Ti, and Zn were determined in the leaves, fruits, and branches of mistletoe, (Viscum albüm L.), used as a medicinal plant, and in the leaves, branches and barks of almond tree which mistletoe grows on. The aim of the study is to investigate whether the mistletoe are more absorbent than the almond tree in terms of the heavy metal contents and the determination of the amount of the elements penetrated into the mistletoe from the almond tree. ICP-MS (inductively coupled plasma-mass spectrometry) was used for the analysis of As, Cd, Mo, and Pb, whereas ICP-OES (inductively coupled plasma optical emission spectrometry) was used for the other elements. The results obtained were statistically evaluated at 95% confidence level. Within the results obtained in this study, it was determined whether there is a significant difference between metal elements in almond tree and mistletoe, or not. As a result, it was observed that there were higher contents of B, Ba, K, Mg, and Zn in the mistletoe than in the almond tree. K was found much higher than other elements in the mistletoe. On the other hand, Al, As, Ca, Cd, Cr, Cu, Fe, Mo, Ni, Sr, Pb, and Ti contents were determined to be more in almond tree than mistletoe.

  11. Simultaneous multi-species determination of trimethyllead, monomethylmercury and three butyltin compounds by species-specific isotope dilution GC-ICP-MS in biological samples.

    PubMed

    Poperechna, Nataliya; Heumann, Klaus G

    2005-09-01

    An accurate and sensitive multi-species species-specific isotope dilution GC-ICP-MS method was developed for the simultaneous determination of trimethyllead (Me3Pb+), monomethylmercury (MeHg+) and the three butyltin species Bu3Sn+, Bu2Sn2+, and BuSn3+ in biological samples. The method was validated by three biological reference materials (CRM 477, mussel tissue certified for butyltins; CRM 463, tuna fish certified for MeHg+; DORM 2, dogfish muscle certified for MeHg+). Under certain conditions, and with minor modifications of the sample pretreatment procedure, this method could also be transferred to environmental samples such as sediments, as demonstrated by analyzing sediment reference material BCR 646 (freshwater sediment, certified for butyltins). The detection limits of the multi-species GC-ICP-IDMS method for biological samples were 1.4 ng g(-1) for MeHg+, 0.06 ng g(-1) for Me3Pb+, 0.3 ng g(-1) for BuSn3+ and Bu3Sn+, and 1.2 ng g(-1) for Bu2Sn2+. Because of the high relevance of these heavy metal alkyl species to the quality assurance of seafood, the method was also applied to corresponding samples purchased from a supermarket. The methylated lead fraction in these samples, correlated to total lead, varied over a broad range (from 0.01% to 7.6%). On the other hand, the MeHg+ fraction was much higher, normally in the range of 80-100%. Considering that we may expect tighter legislative limitations on MeHg+ levels in seafood in the future, we found the highest methylmercury contents (up to 10.6 microg g(-1)) in two shark samples, an animal which is at the end of the marine food chain, whereas MeHg+ contents of less than 0.2 microg g(-1) were found in most other seafood samples; these results correlate with the idea that MeHg+ is usually of biological origin in the marine environment. The concentration of butyltins and the fraction of the total tin content that is from butyltins strongly depend on possible contamination, due to the exclusively anthropogenic

  12. Quantification and visualization of glutathione S-transferase omega 1 in cells using inductively coupled plasma mass spectrometry (ICP-MS) and fluorescence microscopy.

    PubMed

    Liang, Yong; Jiang, Xin; Tang, Nannan; Yang, Limin; Chen, Haifeng; Wang, Qiuquan

    2015-03-01

    We report a novel activity-based and Cu-free click chemistry (CC) mediated methodology for glutathione S-transferase omega 1 (GSTO1) quantification using species-unspecific isotope dilution inductively coupled plasma mass spectrometry (SUID ICP-MS), in which dibenzylcyclooctyne-modified 2-chloroacetamide (DBCO-ChAcA) was designed and synthesized, meanwhile, as a navigator towards GSTO1 for subsequent N3-DOTA-Eu-tagging via Cu-free CC. Using (153)Eu-SUID ICP-MS coupled with size exclusion chromatography (SEC), the LOD (3σ) of GSTO1 reached 6.9 fmol with an RSD of 2.4% at the 0.1 μM level (n = 5) considering the recovery of GSTO1 on the SEC was 96.5 ± 2.4%. The GSTO1 contents in the cells of human hepatocellular carcinoma C7721 and breast carcinoma MCF-7 as well as normal hepatic C7701 without or with cis-platin administration were quantified to be from 1.2 μg/10,000 cells (n = 3, RSD = 4.5%) corresponding to 1.2 × 10(-2) ng per cell to 4.76 μg/10,000 cells (n = 3, RSD = 2.9%) corresponding to 4.76 × 10(-2) ng per cell. For a comparative study, DBCO-ChAcA-fluor 488-based fluorescence microscopy could not alone visualize GSTO1 in the cells but could together with those from the small SH-containing molecules such as GSH and that from extra N3-fluor 488 in the cells. This activity-based CC-mediated tagging/labeling strategy provided an opportunity for ICP-MS-based targeted protein quantification, and is very much expected to find its applications in biological mechanism study and the subsequent drug design.

  13. Determination of Detection Limits and Quantitation Limits for Compounds in a Database of GC/MS by FUMI Theory

    PubMed Central

    Nakashima, Shinya; Hayashi, Yuzuru

    2016-01-01

    The aim of this paper is to propose a stochastic method for estimating the detection limits (DLs) and quantitation limits (QLs) of compounds registered in a database of a GC/MS system and prove its validity with experiments. The approach described in ISO 11843 Part 7 is adopted here as an estimation means of DL and QL, and the decafluorotriphenylphosphine (DFTPP) tuning and retention time locking are carried out for adjusting the system. Coupled with the data obtained from the system adjustment experiments, the information (noise and signal of chromatograms and calibration curves) stored in the database is used for the stochastic estimation, dispensing with the repetition measurements. Of sixty-six pesticides, the DL values obtained by the ISO method were compared with those from the statistical approach and the correlation between them was observed to be excellent with the correlation coefficient of 0.865. The accuracy of the method proposed was also examined and concluded to be satisfactory as well. The samples used are commercial products of pesticides mixtures and the uncertainty from sample preparation processes is not taken into account. PMID:27162706

  14. Inner chromatogram projection (ICP) for resolution of GC-MS data with embedded chromatographic peaks.

    PubMed

    Wang, Zhi-Guo; Chen, Zeng-Ping; Gong, Fan; Wu, Hai-Long; Yu, Ru-Qin

    2002-05-01

    The chromatographic peak located inside another peak in the time direction is called an embedded or inner peak in contradistinction with the embedding peak, which is called an outer peak. The chemical components corresponding to inner and outer peaks are called inner and outer components, respectively. This special case of co-eluting chromatograms was investigated using chemometric approaches taking GC-MS as an example. A novel method, named inner chromatogram projection (ICP), for resolution of GC-MS data with embedded chromatographic peaks is derived. Orthogonal projection resolution is first utilized to obtain the chromatographic profile of the inner component. Projection of the two-way data matrix columnwise-normalized along the time direction to the normalized profile of the inner component found is subsequently performed to find the selective m/z points, if they exist, which represent the chromatogram of the outer component by itself. With the profiles obtained, the mass spectra can easily be found by means of a least-squares procedure. The results for both simulated data and real samples demonstrate that the proposed method is capable of achieving satisfactory resolution performance not affected by the shapes of chromatograms and the relative positions of the components involved.

  15. Non-enzymolytic adenosine barcode-mediated dual signal amplification strategy for ultrasensitive protein detection using LC-MS/MS.

    PubMed

    Yang, Wen; Li, Tengfei; Shu, Chang; Ji, Shunli; Wang, Lei; Wang, Yan; Li, Duo; Mtalimanja, Michael; Sun, Luning; Ding, Li

    2018-05-10

    A method is described for the determination of proteins with LC-MS/MS enabled by a small molecule (adenosine) barcode and based on a double-recognition sandwich structure. The coagulation protein thrombin was chosen as the model analyte. Magnetic nanoparticles were functionalized with aptamer29 (MNP/apt29) and used to capture thrombin from the samples. MNP/apt29 forms a sandwich with functionalized gold nanoparticles modified with (a) aptamer15 acting as thrombin-recognizing element and (b) a large number of adenosine as mass barcodes. The sandwich formed (MNP/apt29-thrombin-apt15/AuNP/adenosine) can ben magnetically separated from the sample. Mass barcodes are subsequently released from the sandwiched structure for further analysis by adding 11-mercaptoundecanoic acid. Adenosine is then detected by LC-MS/MS as it reflects the level of thrombin with impressively amplified signal. Numerous adenosines introduced into the sandwich proportional to the target concentration further amplify the signal. Under optimized conditions, the response is linearly proportional to the thrombin concentration in the range of 0.02 nM to 10 nM, with a detection limit of 9 fM. The application of this method to the determination of thrombin in spiked plasma samples gave recoveries that ranged from 92.3% to 104.7%. Graphical abstract Schematic representation of a method for the determination of thrombin with LC-MS/MS. The method is based on a double-recognition sandwiched structure. With LC-MS/MS, mass barcodes (adenosine) are detected to quantify thrombin, which amplifies the detection signal impressively.

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

    PubMed

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

    2008-10-01

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

  17. 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.

  18. Validation of a highly sensitive ICP-MS method for the determination of platinum in biofluids: application to clinical pharmacokinetic studies with oxaliplatin.

    PubMed

    Morrison, J G; White, P; McDougall, S; Firth, J W; Woolfrey, S G; Graham, M A; Greenslade, D

    2000-12-01

    ELOXATIN (Oxaliplatin) is a novel platinum containing anti-cancer agent with a diaminocyclohexane carrier ligand which has been approved in several major European countries. Clinical studies have demonstrated that the compound exhibits marked activity against colorectal cancers in combination with 5-fluorouracil (5-FU). The aim of this work was to develop and validate a highly sensitive inductively coupled plasma mass spectrometry assay for the determination of oxaliplatin-derived platinum in plasma ultrafiltrate, plasma and whole blood and to apply this technique to clinical pharmacokinetic studies with oxaliplatin. Ultratrace detection of platinum in plasma ultrafiltrate was achieved using ultrasonic nebulisation combined with ICP-MS. This technique allows detection of platinum at the 0.001 microg Pt/ml level in only 100 microl of matrix. Assays in blood and plasma utilised a standard Meinhardt nebuliser and spray chamber, achieving detection limits of 0.1 microg Pt/ml in 100 and 200 microl of matrix, respectively. The assays were validated (accuracy and precision within +/- 15%) over the concentration ranges: 0.001-0.250 microg Pt/ml in plasma ultrafiltrate and 0.1-10 microg Pt/ml for plasma and whole blood. The effect of sample digestion. dilution, long term frozen storage and quantitation in the presence of 5-FU were also investigated and validated. The method was used to monitor platinum exposure following oxaliplatin administration (130 mg/m2) to cancer patients. Following a 2 h i.v. infusion, peak platinum levels declined in a triphasic manner in all blood compartments. Free platinum was detected in plasma ultrafiltrate at low levels (0.001 0.010 microg Pt/ml) for up to 3 weeks. In conclusion, a highly sensitive and specific assay has been developed for the determination of platinum in biofluids. This method enabled characterisation of the long term exposure to platinum in patients following oxaliplatin treatment.

  19. The Influence of Non-spectral Matrix Effects on the Accuracy of Isotope Ratio Measurement by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Barling, J.; Shiel, A.; Weis, D.

    2006-12-01

    Non-spectral interferences in ICP-MS are caused by matrix elements effecting the ionisation and transmission of analyte elements. They are difficult to identify in MC-ICP-MS isotopic data because affected analyses exhibit normal mass dependent isotope fractionation. We have therefore investigated a wide range of matrix elements for both stable and radiogenic isotope systems using a Nu Plasma MC-ICP-MS. Matrix elements commonly enhance analyte sensitivity and change the instrumental mass bias experienced by analyte elements. These responses vary with element and therefore have important ramifications for the correction of data for instrumental mass bias by use of an external element (e.g. Pb and many non-traditional stable isotope systems). For Pb isotope measurements (Tl as mass bias element), Mg, Al, Ca, and Fe were investigated as matrix elements. All produced signal enhancement in Pb and Tl. Signal enhancement varied from session to session but for Ca and Al enhancement in Pb was less than for Tl while for Mg and Fe enhancement levels for Pb and Tl were similar. After correction for instrumental mass fractionation using Tl, Mg effected Pb isotope ratios were heavy (e.g. ^{208}Pb/204Pbmatrix > ^{208}Pb/204Pbtrue) for both moderate and high [Mg] while Ca effected Pb showed little change at moderate [Ca] but were light at high [Ca]. ^{208}Pb/204Pbmatrix - ^{208}Pb/204Pbtrue for all elements ranged from +0.0122 to - 0.0177. Isotopic shifts of similar magnitude are observed between Pb analyses of samples that have seen either one or two passes through chemistry (Nobre Silva et al, 2005). The double pass purified aliquots always show better reproducibility. These studies show that the presence of matrix can have a significant effect on the accuracy and reproducibility of replicate Pb isotope analyses. For non-traditional stable isotope systems (e.g. Mo(Zr), Cd(Ag)), the different responses of analyte and mass bias elements to the presence of matrix can result in del

  20. 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

  1. Characterisation of mineralogical forms of barium and trace heavy metal impurities in commercial barytes by EPMA, XRD and ICP-MS.

    PubMed

    Ansari, T M; Marr, I L; Coats, A M

    2001-02-01

    This study was carried out to characterise the mineralogical forms of barium and the trace heavy metal impurities in commercial barytes of different origins using electron probe microanalysis (EPMA), X-ray diffraction (XRD) and inductively coupled plasma mass spectrometry (ICP-MS). Qualitative EPMA results show the presence of typically eight different minerals in commercial barytes including barite (BaSO4), barium feldspar, galena (PbS), pyrite (FeS2), sphalerite (ZnS), quartz (SiO2), and silicates, etc. Quantitative EPMA confirms that the barite crystals in the barytes contain some strontium and a little calcium, whereas trace heavy metals occur in the associated minerals. Analysis of aqua regia extracts of barytes samples by ICP-MS has shown the presence of a large number of elements in the associated minerals. Arsenic, copper and zinc concentrations correlate closely in all 10 samples. The findings suggest that barytes is not, as traditionally thought, an inert mineral, but is a potentially toxic substance due to its associated heavy metal impurities, which can be determined by an aqua regia digest without the need for complete dissolution of the barite itself. X-ray powder diffraction was not informative as the complex barite pattern masks the very weak lines from the small amounts of associated minerals.

  2. 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.

  3. 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

  4. Silicon Isotopic Measurements in Desolvated Samples by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Cardinal, D.; Alleman, L.; Ziegler, K.; de Jong, J.; Andre, L.

    2002-12-01

    Silicon, the most ubiquitous rock-forming element presents also a key role in biological processes. In particular, its biogeochemical cycle constitutes one of the most challenging issues in recent years due to its close relationship with the carbon cycle in marine environments (Tréguer et al., 1995; Ragueneau et al., 2000). The most recent silicon isotopic investigations on various natural samples have highlighted the great potential of this (palaeo)-proxy for oceanographers (De La Rocha et al., 1997, 1998). Better understanding the silicon isotope fractionation due to various biogeochemical processes can be achieved by facilitating its measurements through MC-ICPMS technique (De La Rocha et al., 2002; Alleman et al., 2002). In this regard we have developed an original method to analyze silicon isotopes under dry plasma conditions. We demonstrate that coupling a Nu Plasma MC-ICP-MS with a Cetac Aridus desolvator allows the rapid acquisition of natural silicon isotope abundances with high sensitivity and accuracy. To adequately correct for the mass fractionation occurring at the interface between the plasma source and the mass spectrometer line, we combine external normalization using Mg as a dopant with standard-sample bracketing using NBS-28 as the reference. With the desolvating nebulization system, the measurement of 28Si and 29Si isotopes is not hampered by significant interferences. δ29Si values are obtained with an accuracy and repeatability better than 0.1 \\permil. The accuracy has been successfully calibrated against the laser fluorination line technique (De La Rocha et al., 1996; Alleman et al., 2002). We could demonstrate that the isotopic fractionation that might occur in the plasma or the desolvator was adequately corrected by combining Mg isotopes and the sample-standard bracketing procedure. Moreover, the preservation of the Si isotopic signatures of the samples is validated by the different chemical sample treatments required by these two

  5. Investigation of the behaviour of zero-valent iron nanoparticles and their interactions with Cd2+ in wastewater by single particle ICP-MS.

    PubMed

    Vidmar, Janja; Oprčkal, Primož; Milačič, Radmila; Mladenovič, Ana; Ščančar, Janez

    2018-04-12

    Zero-valent iron nanoparticles (nZVI) exhibit great potential for the removal of metal contaminants from wastewater. After their use, there is a risk that nZVI will remain dispersed in remediated water and represent potential nano-threats to the environment. Therefore, the behaviour of nZVI after remediation must be explored. To accomplish this, we optimised a novel method using single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) for the sizing and quantification of nZVI in wastewater matrices. H 2 reaction gas was used in MS/MS mode for the sensitive and interference-free determination of low concentrations of nZVI with a low size limit of detection (36nm). This method was applied to study the influence of different iron (Fe) loads (0.1, 0.25, 0.5 and 1.0gL -1 ) and water matrices (Milli-Q water, synthetic and effluent wastewater) on the behaviour of nZVI, their interactions with Cd 2+ and the efficiency of Cd 2+ removal. The aggregation and sedimentation of nZVI increased with settling time. Sedimentation was slower in effluent wastewater than in Milli-Q water or synthetic wastewater. Consequently, Cd 2+ was more efficiently (86%) removed from effluent wastewater than from synthetic wastewater (73%), while its removal from Milli-Q water was inefficient (19%). The trace amounts of Cd 2+ that remained in the remediated water were either dissolved or sorbed to residual nZVI. The results of the nanoremediation of effluent wastewater with varying Fe loads showed that sedimentation was faster at higher initial concentrations of nZVI. After seven days of settling, low concentrations of Fe remained in the effluent wastewater at Fe loads of 0.5gL -1 or higher, which could indicate that the use of nZVI in nanoremediation under the described conditions may not represent an environmental nano-threat. However, further studies are needed to assess the ecotoxicological impact of Fe-related NPs used for the nanoremediation of wastewaters. Copyright © 2018

  6. 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

  7. 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

  8. 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.

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

    PubMed

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

    2003-01-01

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

  10. A fast ultrasound-assisted extraction procedure for trace elements determination in hair samples by ICP-MS for forensic analysis.

    PubMed

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

    2009-11-20

    An ultrasound-assisted extraction method is proposed for the determination of trace elements in hair samples by inductively coupled plasma-mass spectrometry (ICP-MS) for forensic investigation. Prior to analysis, 25mg of hair samples were accurately weighed into (15 mL) conical tubes. Then, 2 mL of 20% HNO(3) is added to the samples, sonicated at 2 min (50W, 100% amplitude), and then further diluted to 10 mL with Milli-Q water. Resulted diluted slurries are centrifuged and the analytes are directly determined in the supernatant. Calibrations against aqueous solutions were carried out with rhodium as internal standard. The method was successfully applied for the extraction of Al, As, Ba, Be, Cd, Co, Cr, Cu, Mn, Pb, Tl, U, V and Zn with a method detection limit (3s, n=20) of 0.1, 0.4, 0.2, 0.09, 0.08, 0.04, 0.1, 2.9, 1.0, 0.9, 0.04, 0.05, 0.1 and 4.2 ng/g, respectively. Method accuracy is traceable to Certified Reference Materials (CRMs) 85 and 86 human hair from the International Atomic Energy Agency (IAEA). Additional validation data are provided based on the analysis of hair samples from the trace elements intercomparison program operated by the Institut National de Sante' Publique du Quebec, Canada. The proposed method is very simple and can be applied for forensic purposes with the elimination of sample digestion step prior to analysis. Then, a considerable improvement in the sample throughput is archived with the use of the proposed method.

  11. Comparision of ICP-OES and MP-AES in determing soil nutrients by Mechlich3 method

    NASA Astrophysics Data System (ADS)

    Tonutare, Tonu; Penu, Priit; Krebstein, Kadri; Rodima, Ako; Kolli, Raimo; Shanskiy, Merrit

    2014-05-01

    Accurate, routine testing of nutrients in soil samples is critical to understanding soil potential fertility. There are different factors which must be taken into account selecting the best analytical technique for soil laboratory analysis. Several techniques can provide adequate detection range for same analytical subject. In similar cases the choise of technique will depend on factors such as sample throughput, required infrastructure, ease of use, used chemicals and need for gas supply and operating costs. Mehlich 3 extraction method is widely used for the determination of the plant available nutrient elements contents in agricultural soils. For determination of Ca, K, and Mg from soil extract depending of laboratory ICP and AAS techniques are used, also flame photometry for K in some laboratories. For the determination of extracted P is used ICP or Vis spectrometry. The excellent sensitivity and wide working range for all extracted elements make ICP a nearly ideal method, so long as the sample throughput is big enough to justify the initial capital outlay. Other advantage of ICP techniques is the multiplex character (simultaneous acquisition of all wavelengths). Depending on element the detection limits are in range 0.1 - 1000 μg/L. For smaller laboratories with low sample throughput requirements the use of AAS is more common. Flame AAS is a fast, relatively cheap and easy technique for analysis of elements. The disadvantages of the method is single element analysis and use of flammable gas, like C2H2 and oxidation gas N2O for some elements. Detection limits of elements for AAS lays from 1 to 1000 μg/L. MP-AES offers a unique alternative to both, AAS and ICP-OES techniques with its detection power, speed of analysis. MP-AES is quite new, simple and relatively inexpensive multielemental technique, which is use self-sustained atmospheric pressure microwave plasma (MP) using nitrogen gas generated by nitrogen generator. Therefore not needs for argon and

  12. Studies on the content of heavy metals in Aries River using ICP-MS

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

    Voica, Cezara, E-mail: Cezara.Voica@itim-cj.ro; Kovacs, Melinda, E-mail: Cezara.Voica@itim-cj.ro; Feher, Ioana, E-mail: Cezara.Voica@itim-cj.ro

    2013-11-13

    Among the industrial branches, the mining industry has always been an important source of environmental pollution, both aesthetically and chemically. Through this paper results of ICP-MS characterization of Aries River Basin are reported. Mining activities from this area has resulted in contamination of environment and its surrounding biota. This is clearly evidenced in analyzed water samples, especially from Baia de Aries site where increased amount of trace elements as Cr, Zn, As, Se, Cd, Pb and U were founded. Also in this site greater amount of rare earth elements was evidenced also. Through monitoring of Aries River from other non-miningmore » area it was observed that the quantitative content of heavy metals was below the maximum permissible levels which made us to conclude that the water table wasn't seriously affected (which possibly might be attributed to the cessation of mining activities in this area from a few years ago)« less

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

    PubMed

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

    2016-01-01

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

  14. Biomonitoring of 37 trace elements in blood samples from inhabitants of northern Germany by ICP-MS.

    PubMed

    Heitland, Peter; Köster, Helmut D

    2006-01-01

    The trace elements Ag, As, Au, B, Ba, Be, Bi, Cd, Ce, Co, Cs, Cu, Ga, Hf, Hg, In, La, Mn, Mo, Ni, Pb, Pd, Rb, Rh, Ru, Sb, Se, Sn, Sr, Te, Th, Tl, U, V, W, Y and Zr were determined in 130 human blood samples from occupationally non-exposed volunteers living in the greater area of Bremen in northern Germany. The blood samples were collected in lithium heparin monovettes developed for trace metal determination and were analysed by inductively coupled plasma mass spectrometry (ICP-MS) with an octopole-based collision/reaction cell. For sample introduction into the ICP, the blood samples were diluted 1/10 (V/V) with a 0.1% Triton-X-100 and 0.5% (V/V) ammonia solution. The method validation of our developed routine method is described for all 37 elements and results about internal and external quality assurance are discussed. Information on exposure conditions of all human subjects were collected by questionnaire-based interviews, including smoking habits, seafood consumption and the type of dental alloys in the teeth. Mean values, geometric mean values, ranges and selected percentiles of all elemental concentrations in human blood are presented, which helps toxicologists and clinical chemists planning research about exposition to metals and health effects caused by exposition to metals.

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

    PubMed

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

    2014-04-01

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

  16. An integrated automatic system to evaluate U and Th dynamic lixiviation from solid matrices, and to extract/pre-concentrate leached analytes previous ICP-MS detection.

    PubMed

    Ceballos, Melisa Rodas; García-Tenorio, Rafael; Estela, José Manuel; Cerdà, Víctor; Ferrer, Laura

    2017-12-01

    Leached fractions of U and Th from different environmental solid matrices were evaluated by an automatic system enabling the on-line lixiviation and extraction/pre-concentration of these two elements previous ICP-MS detection. UTEVA resin was used as selective extraction material. Ten leached fraction, using artificial rainwater (pH 5.4) as leaching agent, and a residual fraction were analyzed for each sample, allowing the study of behavior of U and Th in dynamic lixiviation conditions. Multivariate techniques have been employed for the efficient optimization of the independent variables that affect the lixiviation process. The system reached LODs of 0.1 and 0.7ngkg -1 of U and Th, respectively. The method was satisfactorily validated for three solid matrices, by the analysis of a soil reference material (IAEA-375), a certified sediment reference material (BCR- 320R) and a phosphogypsum reference material (MatControl CSN-CIEMAT 2008). Besides, environmental samples were analyzed, showing a similar behavior, i.e. the content of radionuclides decreases with the successive extractions. In all cases, the accumulative leached fraction of U and Th for different solid matrices studied (soil, sediment and phosphogypsum) were extremely low, up to 0.05% and 0.005% of U and Th, respectively. However, a great variability was observed in terms of mass concentration released, e.g. between 44 and 13,967ngUkg -1 . Copyright © 2017 Elsevier B.V. All rights reserved.

  17. 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.

  18. Influence of metal loading and humic acid functional groups on the complexation behavior of trivalent lanthanides analyzed by CE-ICP-MS.

    PubMed

    Kautenburger, Ralf; Hein, Christina; Sander, Jonas M; Beck, Horst P

    2014-03-13

    The complexation behavior of Aldrich humic acid (AHA) and a modified humic acid (AHA-PB) with blocked phenolic hydroxyl groups for trivalent lanthanides (Ln) is compared, and their influence on the mobility of Ln(III) in an aquifer is analyzed. As speciation technique, capillary electrophoresis (CE) was hyphenated with inductively coupled plasma mass spectrometry (ICP-MS). For metal loading experiments 25 mg L(-1) of AHA and different concentrations (cLn(Eu+Gd)=100-6000 μg L(-1)) of Eu(III) and Gd(III) in 10mM NaClO4 at pH 5 were applied. By CE-ICP-MS, three Ln-fractions, assumed to be uncomplexed, weakly and strongly AHA-complexed metal can be detected. For the used Ln/AHA-ratios conservative complex stability constants log βLnAHA decrease from 6.33 (100 μg L(-1) Ln(3+)) to 4.31 (6000 μg L(-1) Ln(3+)) with growing Ln-content. In order to verify the postulated weaker and stronger humic acid binding sites for trivalent Eu and Gd, a modified AHA with blocked functional groups was used. For these experiments 500 μg L(-1) Eu and 25 mg L(-1) AHA and AHA-PB in 10mM NaClO4 at pH-values ranging from 3 to 10 have been applied. With AHA-PB, where 84% of the phenolic OH-groups and 40% of the COOH-groups were blocked, Eu complexation was significantly lower, especially at the strong binding sites. The log β-values decrease from 6.11 (pH 10) to 5.61 at pH 3 (AHA) and for AHA-PB from 6.01 (pH 7) to 3.94 at pH 3. As a potential consequence, particularly humic acids with a high amount of strong binding sites (e.g. phenolic OH- and COOH-groups) can be responsible for a higher metal mobility in the aquifer due to the formation of dissolved negatively charged metal-humate species. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. 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

  20. Arsenic speciation and fucoxanthin analysis from seaweed dietary supplements using LC-MS.

    PubMed

    Avula, Bharathi; Wang, Yan-Hong; Khan, Ikhlas A

    2015-01-01

    The study involves the analysis of total arsenic (As) in metallic form, and organic and inorganic As species from seaweeds and dietary supplements. The analysis provides data for dietary exposure estimates of inorganic species that are considered more toxic to humans than organic and total As. Total As was determined by acid digestion followed by inductively coupled plasma (ICP)-MS. To characterize the As species, solvent extraction with sonication and microwave extraction using various aqueous and aqueous/organic solvent mixtures were initially evaluated. The optimum As speciation method was determined to be water extraction followed by anion exchange HPLC coupled with ICP-MS. Optimization of chromatographic conditions led to baseline separation for six As species, including As acid, arsenous acid, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, and arsenocholine, in approximately 8 min using gradient elution. Detection limits for all six compounds were in the range of 10-15 ng/mL. The data presented here will be valuable for the QA of analytical method development and surveys of total As and As species in dietary supplements. The most abundant As species found were arsenite [As(III)] and arsenate [As(V)]. The sum of inorganic As species present in the dietary supplements ranged from 1.2 to 31 μg/day. In addition, the dietary supplements purported to contain fucoxanthin, a carotenoid having pharmacological activities, were analyzed using ultra-performance LC-UV/MS.

  1. ICP-MS determination of trace elements in aerosols using a dynamic reaction cell: first results in PM10 comparing road and aerial traffic in Nice area (France).

    PubMed

    Fabretti, Jean-François; Sauret, Nathalie; Gal, Jean-François; Maria, Pierre-Charles; Schärer, Urs

    2007-09-01

    An analytical methodology was developed for the determination of 21 trace elements in suspended particulate matter (PM) using a microwave digestion procedure associated with an inductively coupled plasma mass spectrometry (ICP-MS). The dynamic reaction cell (DRC) of the instrument was carefully optimized to eliminate polyatomic species causing spectral interferences for three specified elements (Cr, Fe, Mn). With this method, the detection limits based on the analysis of seven quartz fibre filters (QFF) considering a one-week sample (250 m3) varied between 0.2 and 650 pg m(-3) for trace elements and between 2.1 and 5.6 ng m(-3) for major elements (Fe, Ti, Zn). The recovery of the analytes was tested with NIST SRM 1648 urban dust within 10% of the certified values only for 3-4 mg of material. The first results were discussed for a field campaign which was carried out simultaneously in the heaviest traffic road tunnel of the centre of Nice and near the landing-taking-off runways in the international airport of Nice Côte d'Azur. The behaviour of some combustion tracers was especially studied.

  2. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  4. Effects of liquid chromatography mobile phases and buffer salts on phosphorus inductively coupled plasma atomic emission and mass spectrometries utilizing ultrasonic nebulization and membrane desolvation.

    PubMed

    Carr, John E; Kwok, Kaho; Webster, Gregory K; Carnahan, Jon W

    2006-01-23

    Atomic spectrometry, specifically inductively coupled plasma atomic emission spectrometry (ICP-AES) and mass spectrometry (ICP-MS) show promise for heteroatom-based detection of pharmaceutical compounds. The combination of ultrasonic nebulization (USN) with membrane desolvation (MD) greatly enhances detection limits with these approaches. Because pharmaceutical analyses often incorporate liquid chromatography, the study herein was performed to examine the effects of solvent composition on the analytical behaviors of these approaches. The target analyte was phosphorus, introduced as phosphomycin. AES response was examined at the 253.7 nm atom line and mass 31 ions were monitored for the MS experiments. With pure aqueous solutions, detection limits of 5 ppb (0.5 ng in 0.1 mL injection volumes) were obtained with ICP-MS. The ICP-AES detection limit was 150 ppb. Solvent compositions were varied from 0 to 80% organic (acetonitrile and methanol) with nine buffers at concentrations typically used in liquid chromatography. In general, solvents and buffers had statistically significant, albeit small, effects on ICP-AES sensitivities. A few exceptions occurred in cases where typical liquid chromatography buffer concentrations produced higher mass loadings on the plasma. Indications are that isocratic separations can be reliably performed. Within reasonable accuracy tolerances, it appears that gradient chromatography can be performed without the need for signal response normalization. Organic solvent and buffer effects were more significant with ICP-MS. Sensitivities varied significantly with different buffers and organic solvent content. In these cases, gradient chromatography will require careful analytical calibration as solvent and buffer content is varied. However, for most buffer and solvent combinations, signal and detection limits are only moderately affected. Isocratic separations and detection are feasible.

  5. Fast and accurate determination of K, Ca, and Mg in human serum by sector field ICP-MS.

    PubMed

    Yu, Lee L; Davis, W Clay; Nuevo Ordonez, Yoana; Long, Stephen E

    2013-11-01

    Electrolytes in serum are important biomarkers for skeletal and cellular health. The levels of electrolytes are monitored by measuring the Ca, Mg, K, and Na in blood serum. Many reference methods have been developed for the determination of Ca, Mg, and K in clinical measurements; however, isotope dilution thermal ionization mass spectrometry (ID-TIMS) has traditionally been the primary reference method serving as an anchor for traceability and accuracy to these secondary reference methods. The sample matrix must be separated before ID-TIMS measurements, which is a slow and tedious process that hindered the adoption of the technique in routine clinical measurements. We have developed a fast and accurate method for the determination of Ca, Mg, and K in serum by taking advantage of the higher mass resolution capability of the modern sector field inductively coupled plasma mass spectrometry (SF-ICP-MS). Each serum sample was spiked with a mixture containing enriched (44)Ca, (26)Mg, and (41)K, and the (42)Ca(+):(44)Ca(+), (24)Mg(+):(26)Mg(+), and (39)K(+):(41)K(+) ratios were measured. The Ca and Mg ratios were measured in medium resolution mode (m/Δm ≈ 4 500), and the K ratio in high resolution mode (m/Δm ≈ 10 000). Residual (40)Ar(1)H(+) interference was still observed but the deleterious effects of the interference were minimized by measuring the sample at K > 100 ng g(-1). The interferences of Sr(++) at the two Ca isotopes were less than 0.25 % of the analyte signal, and they were corrected with the (88)Sr(+) intensity by using the Sr(++):Sr(+) ratio. The sample preparation involved only simple dilutions, and the measurement using this sample preparation approach is known as dilution-and-shoot (DNS). The DNS approach was validated with samples prepared via the traditional acid digestion approach followed by ID-SF-ICP-MS measurement. DNS and digested samples of SRM 956c were measured with ID-SF-ICP-MS for quality assurance, and the results (mean

  6. Determination of iodine and molybdenum in milk by quadrupole ICP-MS.

    PubMed

    Reid, Helen J; Bashammakh, Abdul A; Goodall, Phillip S; Landon, Mark R; O'Connor, Ciaran; Sharp, Barry L

    2008-03-15

    A reliable method for the determination of iodine and molybdenum in milk samples, using alkaline digestion with tetramethylammonium hydroxide and hydrogen peroxide, followed by quadrupole ICP-MS analysis, has been developed and tested using certified reference materials. The use of He+O2 (1.0 ml min(-1) and 0.6 ml min(-1)) in the collision-reaction cell of the mass spectrometer to remove (129)Xe+-- initially to enable the determination of low levels of 129I--also resulted in the quantitative conversion of Mo(+) to MoO2+ which enabled the molybdenum in the milk to be determined at similar mass to the iodine with the use of Sb as a common internal standard. In order to separate and pre-concentrate iodine at sub microg l(-1) concentrations, a novel method was developed using a cation-exchange column loaded with Pd2+ and Ca2+ ions to selectively retain iodide followed by elution with a small volume of ammonium thiosulfate. This method showed excellent results for aqueous iodide solutions, although the complex milk digest matrix made the method unsuitable for such samples. An investigation of the iodine species formed during oxidation and extraction of milk sample digests was carried out with a view to controlling the iodine chemistry.

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

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

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

    2006-05-09

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

  8. Trace metal determination in natural waters by automated solid phase extraction system and ICP-MS: the influence of low level Mg and Ca.

    PubMed

    Wang, Bo-Shian; Lee, Chih-Ping; Ho, Tung-Yuan

    2014-10-01

    A fully automated high pressure pretreatment system with Nobias Chelate-PA1 resin (PA1) was developed for trace metal determination by ICP-MS in natural waters. By varying the concentrations of Mg and Ca to mimic the concentrations in the eluate obtained by PA1 or iminodiacetate type resins, the overall analytical performance of the system was assessed for the determination of Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Cd, Ag, Pb and REE. Comparing with the low mM level Mg and Ca (both ranging from 1 to 4mM) eluted by iminodiacetate type resins, the eluate obtained by PA1 contains sub-μM level Mg and Ca, which remarkably decrease matrix effect in ICP-MS analysis and significantly improve the analytical performance. With recovery better than 90% for most the trace metals examined, the accuracy was further verified through the analysis of five natural water reference materials with salinity spanning from 0 to 35‰. We have successfully applied the pretreatment system to determine trace metals in the seawater samples collected in the Western Philippine Sea through Taiwan GEOTRACES cruise. Copyright © 2014 Elsevier B.V. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  10. Quantitative characterization of TiO2 nanoparticle release from textiles by conventional and single particle ICP-MS

    NASA Astrophysics Data System (ADS)

    Mackevica, Aiga; Olsson, Mikael Emil; Hansen, Steffen Foss

    2018-01-01

    TiO2 is ubiquitously present in a wide range of everyday items, both as an intentionally incorporated additive and naturally occurring constituent. It can be found in a wide range of consumer products, including personal care products, food contact materials, and textiles. Normal use of these products may lead to consumer and/or environmental exposure to TiO2, possibly in form of nanoparticles. The aim of this study is to perform a leaching test and apply state-of-the-art methods to investigate nano-TiO2 and total Ti release from five types of commercially available conventional textiles: table placemats, wet wipes, microfiber cloths, and two types of baby bodysuits, with Ti contents ranging from 2.63 to 1448 μg/g. Released particle analysis was performed using conventional and single particle inductively coupled plasma mass spectrometry (ICP-MS and spICP-MS), in conjunction with transmission electron microscopy (TEM), to measure total and particulate TiO2 release by mass and particle number, as well as size distribution. Less than 1% of the initial Ti content was released over 24 h of leaching, with the highest releases reaching 3.13 μg/g. The fraction of nano-TiO2 released varied among fabric types and represented 0-80% of total TiO2 release. Particle mode sizes were 50-75 nm, and TEM imaging revealed particles in sizes of 80-200 nm. This study highlights the importance of using a multi-method approach to obtain quantitative release data that is able to provide an indication regarding particle number, size distribution, and mass concentration, all of which can help in understanding the fate and exposure of nanoparticles.

  11. Efficient generation of volatile cadmium species using Ti(III) and Ti(IV) and application to determination of cadmium by cold vapor generation inductively coupled plasma mass spectrometry (CVG-ICP-MS)†

    PubMed Central

    Arslan, Zikri; Yilmaz, Vedat; Rose, LaKeysha

    2015-01-01

    In this study, a highly efficient chemical vapor generation (CVG) approach is reported for determination of cadmium (Cd). Titanium (III) and titanium (IV) were investigated for the first time as catalytic additives along with thiourea, L-cysteine and potassium cyanide (KCN) for generation of volatile Cd species. Both Ti(III) and Ti(IV) provided the highest enhancement with KCN. The improvement with thiourea was marginal (ca. 2-fold), while L-cysteine enhanced signal slightly only with Ti(III) in H2SO4. Optimum CVG conditions were 4% (v/v) HCl + 0.03 M Ti(III) + 0.16 M KCN and 2% (v/v) HNO3 + 0.03 M Ti(IV) + 0.16 M KCN with a 3% (m/v) NaBH4 solution. The sensitivity was improved about 40-fold with Ti(III) and 35-fold with Ti(IV). A limit of detection (LOD) of 3.2 ng L−1 was achieved with Ti(III) by CVG-ICP-MS. The LOD with Ti(IV) was 6.4 ng L−1 which was limited by the blank signals in Ti(IV) solution. Experimental evidence indicated that Ti(III) and Ti(IV) enhanced Cd vapor generation catalytically; for best efficiency mixing prior to reaction with NaBH4 was critical. The method was highly robust against the effects of transition metal ions. No significant suppression was observed in the presence of Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II) and Zn(II) up to 1.0 μg mL−1. Among the hydride forming elements, no interference was observed from As(III) and Se(IV) at 0.5 μg mL−1 level. The depressive effects from Pb(II) and Sb(III) were not significant at 0.1 μg mL−1 while those from Bi(III) and Sn(II) were marginal. The procedures were validated with determination of Cd by CVG-ICP-MS in a number certified reference materials, including Nearshore seawater (CASS-4), Bone ash (SRM 1400), Dogfish liver (DOLT-4), Mussel tissue (SRM 2976) and Domestic Sludge (SRM 2781). PMID:26251554

  12. Rapid glucosinolate detection and identification using accurate mass MS-MS

    USDA-ARS?s Scientific Manuscript database

    Currently, there is a demand for accurate evaluation of brassica plat species for their glucosinolate content. An optimized method has been developed for detecting and identifying glucosinolates in plant extracts using MS-MS fragmentation with ion trap collision induced dissociation (CID) and higher...

  13. 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.

  14. Determination of trace heavy metals in harvested rainwater used for drinking in Hebron (south West Bank, Palestine) by ICP-MS.

    PubMed

    Malassa, Husam; Al-Rimawi, Fuad; Al-Khatib, Mahmoud; Al-Qutob, Mutaz

    2014-10-01

    Rainwater samples harvested for drinking from the west part of Hebron (south of West Bank in Palestine), the largest city in the West Bank, were analyzed for the content of different trace heavy metals (Cr, Mn, Co, Ni, Cu, Zn, Mo, Ag, Cd, Bi, and Pb) by inductively coupled plasma mass spectrometry (ICP-MS). This study was conducted to determine the water quality of harvested rainwater used for drinking of south West Bank (case study, Hebron area). A total of 44 water samples were collected in November 2012 from 44 house cisterns used to collect rainwater from the roofs of houses. The samples were analyzed for their pH, temperature, electrical conductivity, total dissolved solids, and different heavy metal contents. The pH of all water samples was within the US Environmental Protection Agency limits (6.5-8.5), while some water samples were found to exceed the allowed WHO limit for total dissolved solids (TDSs) in drinking water. Results showed that concentrations of the heavy metals vary significantly between the 44 samples. Results also showed that the concentration of five heavy metals (Cr, Mn, Ni, Ag, and Pb) is higher than the WHO limits for these heavy metals in drinking water. Overall, our findings revealed that harvested rainwater used for drinking of this part of south West Bank is contaminated with heavy metals that might affect human health.

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

    PubMed

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

    2001-10-20

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

  16. 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.

  17. Detection and quantification of cocaine and benzoylecgonine in meconium using solid phase extraction and UPLC/MS/MS.

    PubMed

    Gunn, Josh; Kriger, Scott; Terrell, Andrea R

    2010-01-01

    The simultaneous determination and quantification of cocaine and its major metabolite, benzoylecgonine, in meconium using UPLC-MS/MS is described. Ultra-performance liquid chromatography (UPLC) is an emerging analytical technique which draws upon the principles of chromatography to run separations at higher flow rates for increased speed, while simultaneously achieving superior resolution and sensitivity. Extraction of cocaine and benzoylecgonine from the homogenized meconium matrix was achieved with a preliminary protein precipitation or protein 'crash' employing cold acetonitrile, followed by a mixed mode solid phase extraction (SPE). Following elution from the SPE cartridge, eluents were dried down under nitrogen, reconstituted in 200 microL of DI water:acetonitrile (ACN) (75:25), and injected onto the UPLC/MS/MS for analysis. The increased speed and separation efficiency afforded by UPLC, allowed for the separation and subsequent quantification of both analytes in less than 2 min. Analytes were quantified using multiple reaction monitoring (MRM) and six-point calibration curves constructed in negative blood. Limits of detection for both analytes were 3 ng/g and the lower limit of quantitation (LLOQ) was 30 ng/g.

  18. Comparison of detection techniques for capillary electrophoresis analysis of gold nanoparticles.

    PubMed

    Matczuk, Magdalena; Aleksenko, Svetlana S; Matysik, Frank-Michael; Jarosz, Maciej; Timerbaev, Andrei R

    2015-05-01

    As metallic nanoparticles are growing in importance as analytes in CE, increases an interest in appropriate detection methods for their quantification in various samples. For gold nanoparticles (AuNPs), the most common UV detection poses intricacy of inadequate sensitivity that hinders the applicability of CE. With the objective of resolving this challenge, UV detection was compared with C(4) D and ICP-MS as alternative modes of detection for AuNPs. A C(4) D detector, applied under pressure-driven conditions, exhibited better sensitivity than a UV detector. However, C(4) D turned to be unsatisfactory to differentiate the signal of AuNPs at common CE conditions despite varying the nature of BGE and detection conditions. Due to intrinsic sensitivity and low background levels typical to Au, ICP-MS greatly surpasses UV detection. After optimization trials, CE-ICP-MS gained the LOD of AuNPs as low as 2 × 10(-15) M, as well as an excellent performance in terms of signal stability and linearity. Also importantly, the optimized BGE appears to be well matched to explore the behavior of AuNPs in biologically relevant systems. This was demonstrated by probing the interaction between AuNPs and the main blood-transporting protein, HSA. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Speciation of inorganic tellurium from seawater by ICP-MS following magnetic SPE separation and preconcentration.

    PubMed

    Huang, Chaozhang; Hu, Bin

    2008-03-01

    A new method was developed for the speciation of inorganic tellurium species in seawater by inductively coupled plasma-MS (ICP-MS) following selective magnetic SPE (MSPE) separation. Within the pH range of 2-9, tellurite (Te(IV)) could be quantitatively adsorbed on gamma-mercaptopropyltrimethoxysilane (gamma-MPTMS) modified silica-coated magnetic nanoparticles (MNPs), while the tellurate (Te(VI)) was not retained and remained in solution. Without filtration or centrifugation, these tellurite-loaded MNPs could be separated easily from the aqueous solution by simply applying external magnetic field. The Te(IV) adsorbed on the MNPs could be recovered quantitatively using a solution containing 2 mol/L HCl and 0.03 mol/L K2Cr2O7. Te(VI) was reduced to Te(IV) by L-cysteine prior to the determination of total tellurium, and its assay was based on subtracting Te(IV) from total tellurium. The parameters affecting the separation were investigated systematically and the optimal separation conditions were established. Under the optimal conditions, the LOD obtained for Te(IV) was 0.079 ng/L, while the precision was 7.0% (C = 10 ng/L, n = 7). The proposed method was successfully applied to the speciation of inorganic tellurium in seawater.

  20. 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

  1. Reversed Phase Column HPLC-ICP-MS Conditions for Arsenic Speciation Analysis of Rice Flour.

    PubMed

    Narukawa, Tomohiro; Matsumoto, Eri; Nishimura, Tsutomu; Hioki, Akiharu

    2015-01-01

    New measurement conditions for arsenic speciation analysis of rice flour were developed using HPLC-ICP-MS equipped with a reversed phase ODS column. Eight arsenic species, namely, arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA), trimethylarsine oxide (TMAO), tetramethylarsonium (TeMA), arsenobetaine (AsB) and arsenocholine (AsC), were separated and determined under the proposed conditions. In particular, As(III) and MMAA and DMAA and AsB were completely separated using a newly proposed eluent containing ammonium dihydrogen phosphate. Importantly, the sensitivity changes, in particular those of As(V) and As(III) caused by coexisting elements and by complex matrix composition, which had been problematical in previously reported methods, were eliminated. The new eluent can be applied to C8, C18 and C30 ODS columns with the same effectiveness and with excellent repeatability. The proposed analytical method was successfully applied to extracts of rice flour certified reference materials.

  2. New Robust Reference Materials for In Situ Single Grain Rutile U-Pb Geochronology and Method Refinements for Detrital Rutile Analysis by LA-MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Parrish, R. R.; Bracciali, L.; Condon, D. J.; Horstwood, M. S.; Najman, Y.

    2012-12-01

    While rutile (TiO2) occurs in the heavy mineral suite of detrital sediments and originates mainly in medium- to high-grade metamorphic and some igneous rocks, there are very few applications of U-Pb dating of rutile to provenance studies; this is due to an overreliance on zircon, low U content of rutile limiting measurement quality by in situ methods, a higher proportion of common Pb relative to zircon, and a lack of widely available good quality reference materials. We have addressed these issues and characterized two ~ 1.8 Ga rutile reference materials by SEM, trace elements, U-Pb ID-TIMS, and intra-grain and inter-grain U-Pb LA-MC-ICP-MS analysis using mixed faraday and multiple ion counting detectors with high sensitivity. We have assessed U-Pb discordance and in situ variations in relative common Pb and age and their bearing on the quality of the reference materials for in situ U-Pb dating. The rutiles (Sugluk-4 and PCA-S207) come from granulite facies belts of the Canadian Shield, namely the northern Cape Smith Belt of Quebec and the Snowbird Tectonic Zone (Sasatchewan). The ID-TIMS data are slightly discordant due to variable common Pb and limited Pb loss; the variation in 6 single grains of Sugluk-4, that we use as the primary reference material, is <1% in 206Pb/238U, and <2% for 207Pb/206Pb (95 % conf.); after common Pb correction these variations are <1%. The measured variations are smaller than in existing reference materials (i.e. R10) in current use. LA-ICP-MC-MS data (n ~ 500 for each) have a reproducibility of 206Pb/238U and 207Pb/206Pb of ~2-4% (at the 2S level), which is only modestly worse than long-term data for multiple zircon standards, this being due to the real variation in measured values arising from limited Pb loss, age variation, and common Pb variability [1]. We have applied our refined method to the provenance of rutile from drainages from British Columbia, Bhutan, and the Brahmaputra River of NE India (predominant rutile ages ~ 50, 15

  3. Determination of toxic and essential trace elements in serum of healthy and hypothyroid respondents by ICP-MS: A chemometric approach for discrimination of hypothyroidism.

    PubMed

    Stojsavljević, Aleksandar; Trifković, Jelena; Rasić-Milutinović, Zorica; Jovanović, Dragana; Bogdanović, Gradimir; Mutić, Jelena; Manojlović, Dragan

    2018-07-01

    Inductively coupled plasma-mass spectrometry ((ICP-MS)) was used to determine three toxic (Ni, As, Cd) and six essential trace elements (Cr, Mn, Co, Cu, Zn, Se) in blood serum of patients with hypothyroidism (Hy group) and healthy people (control group), in order to set the experimental conditions for accurate determination of a unique profile of these elements in hypothyroidism. Method validation was performed with standard reference material of the serum by varying the sample treatment with both standard and collision mode for analysis of elements isotopes. Quadratic curvilinear functions with good performances of models and the lowest detection limits were obtained for 52 Cr, 66 Zn, 75 As, 112 Cd in collision mode, and 55 Mn, 59 Co, 60 Ni, 65 Cu, 78 Se in standard mode. Treatment of serum samples with aqueous solution containing nitric acid, Triton X-100 and n-butanol gave the best results. Chemometric tools were applied for discrimination of patients with hypothyroidism. All nine elements discriminated Hy group of samples with almost the same discriminating power as indicated by their higher values for this group of patients. Statistically significant correlation (p < 0.01) was observed for several elements. Results indicated clear differences in element profile between Hy and control group and it could be used as a unique profile of hypothyroid state. Copyright © 2018 Elsevier GmbH. All rights reserved.

  4. Zwitterion-functionalized polymer microspheres as a sorbent for solid phase extraction of trace levels of V(V), Cr(III), As(III), Sn(IV), Sb(III) and Hg(II) prior to their determination by ICP-MS.

    PubMed

    Jia, Xiaoyu; Gong, Dirong; Zhao, Junyi; Ren, Hongyun; Wang, Jiani; Zhang, Xian

    2018-03-19

    This paper describes the preparation of zwitterion-functionalized polymer microspheres (ZPMs) and their application to simultaneous enrichment of V(V), Cr(III), As(III), Sn(IV), Sb(III) and Hg(II) from environmental water samples. The ZPMs were prepared by emulsion copolymerization of ethyl methacrylate, 2-diethylaminoethyl methacrylate and triethylene glycol dimethyl acrylate followed by modification with 1,3-propanesultone. The components were analyzed by elemental analyses as well as Fourier transform infrared spectroscopy, and the structures were characterized by scanning electron microscopy and transmission electron microscopy. The ZPMs were packed into a mini-column for on-line solid-phase extraction (SPE) of the above metal ions. Following extraction with 40 mM NH 4 NO 3 and 0.5 M HNO 3 solution, the ions were quantified by ICP-MS. Under the optimized conditions, the enrichment factors (from a 40 mL sample) are up to 60 for the ions V(V), As(III), Sb(III) and Hg(II), and 55 for Cr(III) and Sn(IV). The detection limits are 1.2, 3.4, 1.0, 3.7, 2.1 and 1.6 ng L -1 for V(V), Cr(III), As(III), Sn(IV), Sb(III) and Hg(II), respectively, and the relative standard deviations (RSDs) are below 5.2%. The feasibility and accuracy of the method were validated by successfully analyzing six certified reference materials as well as lake, well and river waters. Graphical abstract Zwitterion-functionalized polymer microspheres (ZPMs) were prepared and packed into a mini-column for on-line solid-phase extraction (SPE) via pump 1. Then V(V), Cr(III), As(III), Sn(IV), Sb(III) and Hg(II) ions in environmental waters were eluted and submitted to ICP-MS via pump 2.

  5. A comparison of the metal content of some benthic species from coastal waters of the Florida panhandle using high-resolution inductively coupled plasma mass spectrometry (ICP-MS) analysis.

    PubMed

    Philp, R B; Leung, F Y; Bradley, C

    2003-02-01

    Benthic marine invertebrates, sediment, and water from several locations along the Florida panhandle coast from St. Joseph Bay in the west to the mouth of the Wakulla River in the east, including from several river estuaries, were analyzed by double focusing ICP-MS (Finnigan MAT ELEMENT) for Cd, Hg, Pb, Cu, Zn, and As. All were detected in all samples. Sponges generally contained higher levels of Cd than other species. Microciona prolifera sponges from St. Joseph Bay had higher As levels (8.1-13.6 microg/g dry weight) than sponges collected from Dickerson Bay or Appalachee Bay (2.20-9.7) and higher Cd levels (0.43-0.73) than that of a single Microciona specimen collected from Dickerson Bay (0.29). Water content of As was about 20-30x higher in St. Joseph Bay than in any other location, and sediment levels of Cd were about 9x higher. Cu and Zn were higher in organic sediment from St. Joseph Bay than they were in other areas. The Pb content of several sponge species and two of tunicates was considerably higher than in other species. The uptake of most metals in this study (except As) appeared to be affected by the metal, genus, species, and location as much as by levels in either water or sediment. In general, sponges and tunicates seemed to accumulate higher levels than most other species, possibly a function of high filtration rates. The ICP-MS method is useful for environmental studies, but the instrument requires considerable maintenance.

  6. 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

  7. Assessment of skin exposure to nickel, chromium and cobalt by acid wipe sampling and ICP-MS.

    PubMed

    Lidén, Carola; Skare, Lizbet; Lind, Birger; Nise, Gun; Vahter, Marie

    2006-05-01

    There is a great need to accurately assess skin exposure to contact allergens. We have developed a technique for assessment of skin exposure to nickel, chromium and cobalt using acid wipe sampling by cellulose wipes with 1% nitric acid. Chemical analysis was performed by inductively coupled plasma mass spectrometry (ICP-MS). The recovery of nickel, chromium and cobalt from arms and palms was 93%. The analytical result is expressed in terms of mass per unit area (microg/cm(2)). The developed acid wipe sampling technique is suitable for determination of nickel, chromium and cobalt deposited on the skin. The technique may be used in workplace studies, in studies of individuals in the general population, in dermatitis patients, in identification of risk groups, as well as in developing preventive strategies and in follow-up after intervention.

  8. Precise Analysis of Gallium Isotopic Composition by MC-ICP-MS.

    PubMed

    Yuan, Wei; Chen, Jiu Bin; Birck, Jean-Louis; Yin, Zuo Ying; Yuan, Sheng Liu; Cai, Hong Ming; Wang, Zhong Wei; Huang, Qiang; Wang, Zhu Hong

    2016-10-04

    Though an isotope approach could be beneficial for better understanding the biogeochemical cycle of gallium (Ga), an analogue of the monoisotopic element aluminum (Al), the geochemistry of Ga isotopes has not been widely elaborated. We developed a two-step method for purifying Ga from geological (biological) samples for precise measurement of Ga isotope ratio using multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS). Ga was thoroughly separated from other matrix elements using two chromatographic columns loaded with AG 1-X4 and Ln-spec resin, respectively. The separation method was carefully calibrated using both synthetic and natural samples and validated by assessing the extraction yield (99.8 ± 0.8%, 2SD, n = 23) and the reproducibility (2SD uncertainty better than 0.05‰, n = 116) of the measured isotopic ratio (expressed as δ 71 Ga). The validation of the whole protocol, together with instrumental analysis, was confirmed by the investigation of the matrix effect, the result of a standard addition experiment, and the comparison of Ga isotope measurement on two mass spectrometers-Nu Plasma II and Neptune Plus. Although the measurements using the sample-standard bracketing (SSB) correction method on both instruments resulted in identical δ 71 Ga values for reference materials, the modified empirical external normalization (MEEN) method gave relatively better precision compared to SSB on Neptune. Our preliminary results showed large variation of δ 71 Ga (up to 1.83‰) for 10 standards, with higher values in industrially produced materials, implying potential application of Ga isotopes.

  9. Separation of silver ions and starch modified silver nanoparticles using high performance liquid chromatography with ultraviolet and inductively coupled mass spectrometric detection

    NASA Astrophysics Data System (ADS)

    Hanley, Traci A.; Saadawi, Ryan; Zhang, Peng; Caruso, Joseph A.; Landero-Figueroa, Julio

    2014-10-01

    The production of commercially available products marketed to contain silver nanoparticles is rapidly increasing. Species-specific toxicity is a phenomenon associated with many elements, including silver, making it imperative to develop a method to identify and quantify the various forms of silver (namely, silver ions vs. silver nanoparticles) possibly present in these products. In this study a method was developed using high performance liquid chromatography (HPLC) with ultraviolet (UV-VIS) and inductively coupled mass spectrometric (ICP-MS) detection to separate starch stabilized silver nanoparticles (AgNPs) and silver ions (Ag+) by cation exchange chromatography with 0.5 M nitric acid mobile phase. The silver nanoparticles and ions were baseline resolved with an ICP-MS response linear over four orders of magnitude, 0.04 mg kg- 1 detection limit, and 90% chromatographic recovery for silver solutions containing ions and starch stabilized silver nanoparticles smaller than 100 nm.

  10. 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.

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

    PubMed

    Scarciglia, Fabio; Barca, Donatella

    2017-04-01

    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.

  12. 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.

  13. 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.

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

    PubMed Central

    2012-01-01

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

  15. 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.

  16. Aqueous and solid phase speciation of arsenic in a Bengali aquifer using IC-ICP-MS and EXAFS

    NASA Astrophysics Data System (ADS)

    Gault, A. G.; Davidson, L. E.; Lythgoe, P. R.; Charnock, J. M.; Chatterjee, D.; Abou-Shakra, F. R.; Walker, H. J.; Polya, D. A.

    2003-04-01

    Contamination of groundwater and drinking water supplies with arsenic has been reported in many parts of the world and constitutes a serious public health threat. Nowhere is this more apparent than in West Bengal and Bangladesh where arsenic concentrations exceed both World Health Organisation (WHO) and national limits in drinking water supplies leading to what has been described as the worst mass poisoning of a human population in history. Knowledge of both aqueous and solid phase speciation of arsenic in such hazardous arsenic-rich groundwaters is crucial to understanding the processes controlling arsenic release. We report here preliminary work involving the determination of dissolved arsenic speciation in West Bengali groundwaters and extended X-ray absorption fine structure (EXAFS) analysis of the associated sediment. Groundwater samples collected from Nadia district, West Bengal were analysed for arsenic speciation by ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS) within 14 days of collection. Total arsenic concentrations exceeding 850 ug/L were determined; inorganic arsenic constituted the bulk of the dissolved arsenic burden with As(III) as the dominant form. Minor amounts of methylated arsenicals were also detected, however, their concentration did not exceed 5 ug/L. The local coordination environment of arsenic in sediment associated with such groundwaters was probed using K-edge As EXAFS. This revealed that arsenic exists predominantly in its oxidised form, As(V), most likely adsorbed as bidentate arsenate tetrahedra on metal (Fe and/or Al) oxide/hydroxide surfaces, although incorporation of arsenic into a metal oxide structure cannot be unequivocally ruled out. Arsenic was found to occur in several different coordination environments and this, together with the low concentration (< 5 ug/g) of arsenic in the sediment, prevented the unambiguous assignment of the second coordination sphere. The analysis of the trends of key

  17. [Determination of trace heavy metal elements in cortex Phellodendron chinense by ICP-MS after microwave-assisted digestion].

    PubMed

    Kou, Xing-Ming; Xu, Min; Gu, Yong-Zuo

    2007-06-01

    An inductively coupled plasma mass spectrometry (ICP-MS) for determination of the contents of 8 trace heavy metal elements in cortex Phellodendron chinense after microwave-assisted digestion of the sample has been developed. The accuracy of the method was evaluated by the analysis of corresponding trace heavy metal elements in standard reference materials (GBW 07604 and GBW 07605). By applying the proposed method, the contents of 8 trace heavy metal elements in cortex Phellodendron chinense cultivated in different areas (in Bazhong, Yibin and Yingjing, respectively) of Sichuan and different growth period (6, 8 and 10 years of samples from Yingjing) were determined. The relative standard deviation (RSD) is in the range of 3.2%-17.8% and the recoveries of standard addition are in the range of 70%-120%. The results of the study indicate that the proposed method has the advantages of simplicity, speediness and sensitivity. It is suitable for the determination of the contents of 8 trace heavy metal elements in cortex Phellodendron chinense. The results also show that the concentrations of 4 harmful trace heavy metal elements As, Cd, Hg and Pb in cortex Phellodendron chinense are all lower than the limits of Chinese Pharmacopoeia and Green Trade Standard for Importing and Exporting Medicinal Plant and Preparation. Therefore, the cortex Phellodendron chinense is fit for use as medicine and export.

  18. Correlating Cu-sulfide and Au mineralization in the Ertsberg-Grasberg District using LA-ICP-MS and HRXCT

    NASA Astrophysics Data System (ADS)

    Wright, K. A.; Miller, N. R.; Ketcham, R. A.; Kyle, R.

    2016-12-01

    The Ertsberg-Grasberg district in Papua, Indonesia, hosts to two of the largest intrusion-related Cu-Au deposits in the world: the Ertsberg East Skarn system and the Grasberg Intrusive Complex. Cu mineralization within the Grasberg porphyry and Ertsberg skarn systems primarily consists of bornite and chalcopyrite, with minor digenite and idiate. Native Au is commonly found in association with Cu mineralization where Au occurs as inclusions within or immediately proximal to primary Cu-sulfide minerals. At hydrothermal-ore forming temperatures, approximately 400° to 700° C, bornite and chalcopyrite can host up to 1800 ppm Au within the Cu-sulfide lattice. Upon retrograde cooling of the hydrothermal system, the ability of bornite and chalcopyrite to host Au decreases significantly to about 10 ppm, indicating that the Au could be expulsed from the sulfide lattice. Given the close association of native Au and Cu-sulfide concentrations, it is possible that native gold grains form as the Au emerges from the Cu-sulfides. Constraining the genetic and spatio-temporal relationship between Cu-sulfide and Au mineralization within these deposits is of significant interest with regard to the geometallurgical processing of the ore, and to future exploration. This study seeks to evaluate this relationship using High Resolution X-ray Computed Tomography (HRXCT) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). Previous HRXCT studies on Ertsberg-Grasberg ore samples have identified numerous occurrences of native Au grains at the edges of Cu-sulfide masses. HRXCT data are used here to construct 3D Voronoi regions of potential Au "diffusional drainage" from within the Cu-sulfides, where the expectation is a positive correlation between Au grain size and modified Voronoi polyhedron volume, defined as the volume of sulfide closer to that grain than any other via a connected path through sulfide. LA-ICP-MS data are used to determine variations in Au contents

  19. 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.

  20. Nanoscale Coloristic Pigments: Upper Limits on Releases from Pigmented Plastic during Environmental Aging, In Food Contact, and by Leaching.

    PubMed

    Neubauer, Nicole; Scifo, Lorette; Navratilova, Jana; Gondikas, Andreas; Mackevica, Aiga; Borschneck, Daniel; Chaurand, Perrine; Vidal, Vladimir; Rose, Jerome; von der Kammer, Frank; Wohlleben, Wendel

    2017-10-17

    The life cycle of nanoscale pigments in plastics may cause environmental or human exposure by various release scenarios. We investigated spontaneous and induced release with mechanical stress during/after simulated sunlight and rain degradation of polyethylene (PE) with organic and inorganic pigments. Additionally, primary leaching in food contact and secondary leaching from nanocomposite fragments with an increased surface into environmental media was examined. Standardized protocols/methods for release sampling, detection, and characterization of release rate and form were applied: Transformation of the bulk material was analyzed by Scanning Electron Microscopy (SEM), X-ray-tomography and Fourier-Transform Infrared spectroscopy (FTIR); releases were quantified by Inductively Coupled Plasma Mass Spectrometry (ICP-MS), single-particle-ICP-MS (sp-ICP-MS), Transmission Electron Microscopy (TEM), Analytical Ultracentrifugation (AUC), and UV/Vis spectroscopy. In all scenarios, the detectable particulate releases were attributed primarily to contaminations from handling and machining of the plastics, and were not identified with the pigments, although the contamination of 4 mg/kg (Fe) was dwarfed by the intentional content of 5800 mg/kg (Fe as Fe 2 O 3 pigment). We observed modulations (which were at least partially preventable by UV stabilizers) when comparing as-produced and aged nanocomposites, but no significant increase of releases. Release of pigments was negligible within the experimental error for all investigated scenarios, with upper limits of 10 mg/m 2 or 1600 particles/mL. This is the first holistic confirmation that pigment nanomaterials remain strongly contained in a plastic that has low diffusion and high persistence such as the polyolefin High Density Polyethylene (HDPE).

  1. Evaluation of UV-fs-LA-MC-ICP-MS for precise in situ copper isotopic microanalysis of cubanite.

    PubMed

    Ikehata, Kei; Hirata, Takafumi

    2013-01-01

    We evaluated the capabilities of an in situ method for measuring copper isotopes of cubanite using UV-fs-LA-MC-ICP-MS. A comparison of the UV-fs laser results with those obtained from the NIR-fs laser system shows that there is obviously an improvement in the precision (<0.10‰, 2SE) when using the UV-fs laser. In both wavelength modes, matrix-matched standards are required for reliable in situ copper isotope analysis of cubanite. This method was applied to determinations for copper isotopes of minute cubanite grains in a skarn ore. Copper isotopic ratios of cubanite grains near a weathered surface of the sample are lower than those of intact cubanite grains within the sample, suggesting that selective leaching of heavier copper isotope in primary minerals occurred during weathering.

  2. 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.

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

    PubMed

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

    2016-07-01

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

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

    PubMed

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

    2016-01-01

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

  5. 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

  6. Comprehensive Isotopic and Elemental Analysis of a Multi-Oxide Glass By Multicollector ICP-MS in Isotope Substitution Studies

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

    v, Mitroshkov; JV, Ryan

    2016-04-07

    Multicollector ICP-MS was used to comprehensively analyze different types of isotopically-modified glass created in order to investigate the processes of glass corrosion in the water. The analytical methods were developed for the analyses of synthesized, isotopically-modified solid glass and the release of glass constituents upon contact with deionized water. To validate the methods, results from an acid digestion sample of the Analytical Reference Glass (ARG) showed good agreement when compared to data from multiple prior analyses on the same glass [Smith-1]. In this paper, we present the results of this comprehensive analysis from the acid digestion of six types ofmore » isotopically-modified glass and the release of glass constituents into water corrosion after one year of aqueous corrosion.« less

  7. Multi-elements determination in medical and edible Alpinia oxyphylla and Morinda officinalis and their decoctions by ICP-MS.

    PubMed

    Zhao, Xiangsheng; Wei, Jianhe; Shu, Xiaoyan; Kong, Weijun; Yang, Meihua

    2016-12-01

    Contents of twenty elements (Mg, K, Ca, Na, Fe, Al, Zn, Ba, Mn, Cu, Mo, Cr, Ni, As, Se, Cd, Hg, Tl, Pb and V) in two medical and edible plant species, Alpinia oxyphylla and Morinda officinalis were simultaneously determined by inductively coupled plasma-mass spectrometry (ICP-MS) method after microwave digestion with HNO 3 -H 2 O 2 (6:1, v/v) as the digestion solvent. Certified standard reference material Poplar leaf was used to assess the accuracy of the method. The greatest contents of Mg, K, Ca, Al, Fe and Na were found in dried Alpinia oxyphylla and Morinda officinalis samples. The contents of five heavy metals including Pb, Cd, As, Hg and Cu in Alpinia oxyphylla did not exceed the limits. The contents of Pb in 76.67% samples and Cd in two batches of Morinda officinalis samples exceeded the limits set by Chinese Pharmacopeia. The contents of the selected elements in different parts (leaves, stems, roots and fruits) of Alpinia oxyphylla varied considerably. The highest concentrations of Mg, Ca, Mn and Se were found in the leaves of Alpinia oxyphylla, at the same time, while, the contents of 9 elements including Cd, Cr, Cu, As, Pb in the roots were the highest. The transfer ratios of selected elements from both species of herbs into their decoctions were reduced. Especially for the heavy metals, the transfer ratios were below 30% except As (79.73%) in Morinda officinalis. The results showed that decoction of the samples may reduce the intake of heavy metals. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Analysis of high-purity germanium dioxide by ETV-ICP-AES with preliminary concentration of trace elements.

    PubMed

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

    2016-08-01

    The paper presents a combined technique of germanium dioxide analysis by inductively coupled plasma atomic emission spectrometry (ICP-AES) with preconcentration of trace elements by distilling off matrix and electrothermal (ETV) introduction of the trace elements concentrate into the ICP. Evaluation of metrological characteristics of the developed technique of high-purity germanium dioxide analysis was performed. The limits of detection (LODs) for 25 trace elements ranged from 0.05 to 20ng/g. The accuracy of proposed technique is confirmed by "added-found" («or spiking») experiment and comparing the results of ETV-ICP-AES and ICP-AES analysis of high purity germanium dioxide samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Preconcentration and determination of rare-earth elements in iron-rich water samples by extraction chromatography and plasma source mass spectrometry (ICP-MS).

    PubMed

    Hernández González, Carolina; Cabezas, Alberto J Quejido; Díaz, Marta Fernández

    2005-11-15

    A 100-fold preconcentration procedure based on rare-earth elements (REEs) separation from water samples with an extraction chromatographic column has been developed. The separation of REEs from matrix elements (mainly Fe, alkaline and alkaline-earth elements) in water samples was performed loading the samples, previously acidified to pH 2.0 with HNO(3), in a 2ml column preconditioned with 20ml 0.01M HNO(3). Subsequently, REEs were quantitatively eluted with 20ml 7M HNO(3). This solution was evaporated to dryness and the final residue was dissolved in 10ml 2% HNO(3) containing 1mugl(-1) of cesium used as internal standard. The solution was directly analysed by inductively coupled plasma mass spectrometry (ICP-MS), using ultrasonic nebulization, obtaining quantification limits ranging from 0.05 to 0.10 ngl(-1). The proposed method has been applied to granitic waters running through fracture fillings coated by iron and manganese oxy-hydroxides in the area of the Ratones (Cáceres, Spain) old uranium mine.

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

    PubMed

    Schenk, Emily R; Almirall, José R

    2012-04-10

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

  11. 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.

  12. [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.

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

    PubMed

    Pramann, Axel; Rienitz, Olaf

    2016-06-07

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

  14. Discrimination of the Cigarettes Geographical Origin by DRC-ICP-MS Measurements of Pb Isotope Compositions

    NASA Astrophysics Data System (ADS)

    Guo, W.; Hu, S.; Jin, L.

    2014-12-01

    Trace Pb are taken up with the same isotopic ratios as is present in the source soil, and the isotopic composition of Pb could used to reflect these sources and provide powerful indicators of the geographic origin of agriculture products derived from vegetative matter. We developed a simple and high throughput method, which based on DRC-ICP-MS for determination of Pb isotope ratios for discriminating the geographic origin of cigarettes. After acid digestion procedure, the cigarette digested solutions were directly analyzed by ICP-QMS with a DRC pressurized by the non-reactive gas Ne. In the DRC, Ne molecules collision with Pb ions and improves Pb isotope ratios precision 3-fold, which may be due to the collisional dampling smoothes out the ion beam fluctuations. Under the optimum DRC rejection parameter Q (RPq = 0.45), the main matrix components (K, Na, Ca, Mg, Al, Fe etc.) originating from cigarettes were filtered out. Mass discrimination of 208Pb/206Pb ratio in Ne DRC mode increased 0.3% compared to the standard mode, the mass bias due to the in-cell Ne gas collision can be accurately corrected by NIST 981 Pb isotope standard. This method was verified by a tobacco reference material CTV-OTL-2. Results of 208Pb/206Pb and 207Pb/206Pb were 2.0848 ± 0.0028 (2δ) and 0.8452 ± 0.0011 (2δ) for CTA-VTL-2, which were agreed with the literature values (208Pb/206Pb = 2.0884 ± 0.0090 and 207Pb/206Pb = 0.8442 ± 0.0032). The precision of Pb isotope ratios (208Pb/206Pb and 207Pb/206Pb) for the cigarette samples are ranged from 0.01 to 0.08% (N = 5). It has sufficient precision to discriminate 91 different brand cigarettes originated from four different geographic regions (Shown in Fig).

  15. Development of the GC-MS organic aerosol monitor (GC-MS OAM) for in-field detection of particulate organic compounds

    NASA Astrophysics Data System (ADS)

    Cropper, Paul M.; Overson, Devon K.; Cary, Robert A.; Eatough, Delbert J.; Chow, Judith C.; Hansen, Jaron C.

    2017-11-01

    Particulate matter (PM) is among the most harmful air pollutants to human health, but due to its complex chemical composition is poorly characterized. A large fraction of PM is composed of organic compounds, but these compounds are not regularly monitored due to limitations in current sampling and analysis techniques. The Organic Aerosol Monitor (GC-MS OAM) combines a collection device with thermal desorption, gas chromatography and mass spectrometry to quantitatively measure the carbonaceous components of PM on an hourly averaged basis. The GC-MS OAM is fully automated and has been successfully deployed in the field. It uses a chemically deactivated filter for collection followed by thermal desorption and GC-MS analysis. Laboratory tests show that detection limits range from 0.2 to 3 ng for 16 atmospherically relevant compounds, with the possibility for hundreds more. The GC-MS OAM was deployed in the field for semi-continuous measurement of the organic markers, levoglucosan, dehydroabietic acid, and polycyclic aromatic hydrocarbons (PAHs) from January to March 2015. Results illustrate the significance of this monitoring technique to characterize the organic components of PM and identify sources of pollution.

  16. One-milliliter wet-digestion for inductively coupled plasma mass spectrometry (ICP-MS): determination of platinum-DNA adducts in cells treated with platinum(II) complexes.

    PubMed

    Yamada, Kanae; Kato, Naoyuki; Takagi, Akimitsu; Koi, Minoru; Hemmi, Hiromichi

    2005-08-01

    Platinum (Pt)-DNA adducts formed by the anti-tumor agent cisplatin are recognized by the DNA mismatch repair (MMR) system. To investigate the involvement of MMR proteins including hMLH1 in the removal of these adducts, we developed a mL-scale wet-digestion method for inductively coupled plasma mass spectrometry (ICP-MS). The detection limit was 0.01 ng mL(-1) Pt, which corresponded to 2 pg Pt/microg DNA when 10 microg of DNA was used. The mean relative errors were 5.4% or better for a dynamic range of 0.01-10 ng mL(-1) Pt. DNA (approximately 500 microg) had no matrix effect. To improve the accuracy, DNA preparations were treated with ribonuclease and the apparent reduction in the concentration of Pt was corrected using cellular DNA levels, which were determined with Hoechst 33258. No significant differences were observed, in terms of the formation of Pt-DNA adducts or their removal over 6 h, between hMLH1-deficient HCT116 cells, a human colorectal cancer cell line, and hMLH1-complemented HCT116+ch3 cells (n=5; P>0.05), indicating that the hMLH1-dependent DNA repair systems contribute to neither the formation nor the removal of the adducts at detectable levels. In addition, approximately 19% of the adducts were removed within 6 h in both cell lines. A time course analysis (~24 h) suggested that the removal of cisplatin-generated Pt-DNA adducts follows first-order kinetics (t(1/2)=32 h). The amount of Pt-DNA adduct formed by oxaliplatin in 1 h was 56% (ratio of means) of that generated by an equimolar concentration of cisplatin in HCT116. The proposed procedure could be useful for determining Pt-DNA adducts formed by Pt(II) complexes.

  17. ICPD-a new peak detection algorithm for LC/MS.

    PubMed

    Zhang, Jianqiu; Haskins, William

    2010-12-01

    The identification and quantification of proteins using label-free Liquid Chromatography/Mass Spectrometry (LC/MS) play crucial roles in biological and biomedical research. Increasing evidence has shown that biomarkers are often low abundance proteins. However, LC/MS systems are subject to considerable noise and sample variability, whose statistical characteristics are still elusive, making computational identification of low abundance proteins extremely challenging. As a result, the inability of identifying low abundance proteins in a proteomic study is the main bottleneck in protein biomarker discovery. In this paper, we propose a new peak detection method called Information Combining Peak Detection (ICPD ) for high resolution LC/MS. In LC/MS, peptides elute during a certain time period and as a result, peptide isotope patterns are registered in multiple MS scans. The key feature of the new algorithm is that the observed isotope patterns registered in multiple scans are combined together for estimating the likelihood of the peptide existence. An isotope pattern matching score based on the likelihood probability is provided and utilized for peak detection. The performance of the new algorithm is evaluated based on protein standards with 48 known proteins. The evaluation shows better peak detection accuracy for low abundance proteins than other LC/MS peak detection methods.

  18. ICPD-A New Peak Detection Algorithm for LC/MS

    PubMed Central

    2010-01-01

    Background The identification and quantification of proteins using label-free Liquid Chromatography/Mass Spectrometry (LC/MS) play crucial roles in biological and biomedical research. Increasing evidence has shown that biomarkers are often low abundance proteins. However, LC/MS systems are subject to considerable noise and sample variability, whose statistical characteristics are still elusive, making computational identification of low abundance proteins extremely challenging. As a result, the inability of identifying low abundance proteins in a proteomic study is the main bottleneck in protein biomarker discovery. Results In this paper, we propose a new peak detection method called Information Combining Peak Detection (ICPD ) for high resolution LC/MS. In LC/MS, peptides elute during a certain time period and as a result, peptide isotope patterns are registered in multiple MS scans. The key feature of the new algorithm is that the observed isotope patterns registered in multiple scans are combined together for estimating the likelihood of the peptide existence. An isotope pattern matching score based on the likelihood probability is provided and utilized for peak detection. Conclusions The performance of the new algorithm is evaluated based on protein standards with 48 known proteins. The evaluation shows better peak detection accuracy for low abundance proteins than other LC/MS peak detection methods. PMID:21143790

  19. Determination of trace amounts of rare-earth elements in highly pure neodymium oxide by sector field inductively coupled plasma mass spectrometry (ICP-SFMS) and high-performance liquid chromatography (HPLC) techniques

    NASA Astrophysics Data System (ADS)

    Pedreira, W. R.; Sarkis, J. E. S.; da Silva Queiroz, C. A.; Rodrigues, C.; Tomiyoshi, I. A.; Abrão, A.

    2003-02-01

    Recently rare-earth elements (REE) have received much attention in fields of geochemistry and industry. Rapid and accurate determinations of them are increasingly required as industrial demands expand. Sector field inductively coupled plasma mass spectrometry (ICP-SFMS) with high-performance liquid chromatography (HPLC) has been applied to the determination of REE. HR ICP-MS was used as an element-selective detector for HPLC in highly pure materials. The separation of REE with HPLC helped to avoid erroneous analytical results due to spectral interferences. Sixteen elements (Sc, Y and 14 lanthanides) were determined selectively with the HPLC/ICP-SFMS system using a concentration gradient methods. The detection limits with the HPLC/ICP-SFMS system were about 0.5-10 pg mL-1. The percentage recovery ranged from 90% to 100% for different REE. The %RSD of the methods varying between 2.5% and 4.5% for a set of five (n=5) replicates was found for the IPEN's material and for the certificate reference sample. Determination of trace REEs in two highly pure neodymium oxides samples (IPEN and Johnson Matthey Company) were performed. In short, the IPEN's materials which are highly pure (>99.9%) were successfully analyzed without spectral interferences.

  20. The use of Endopep-MS to detect multiple subtypes of botulinum neurotoxins A, B, E, and F

    NASA Astrophysics Data System (ADS)

    Kalb, Suzanne R.; Smith, Theresa J.; Moura, Hercules; Hill, Karen; Lou, Jianlong; Geren, Isin N.; Garcia-Rodriguez, Consuelo; Marks, James D.; Smith, Leonard A.; Pirkle, James L.; Barr, John R.

    2008-12-01

    Botulinum neurotoxins (BoNTs) cause the disease botulism, which can be lethal if untreated. Rapid determination of exposure to BoNT is an important public health goal. Previous work in our laboratory focused on the development of Endopep-MS, a mass spectrometry-based endopeptidase method for detecting and differentiating BoNT A-G in buffer and BoNT A, B, E, and F in clinical samples. We introduce here the use of Endopep-MS to detect non-commercial subtypes of BoNT A, B, E, and F which have been associated with botulism outbreaks. We have now tested and successfully detected 15 of the 17 known subtypes of BoNT A, B, E, and F by Endopep-MS. Extraction of BoNT A and B from a complex mixture prior to analysis is accomplished by using monoclonal antibodies specific for the catalytically inactive heavy chain of the toxin. These antibodies have high-binding affinities and do not interfere with the catalytic activity of the light chain resulting in a lower limit of detection for BoNT A and B than previously reported. We also report for the first time limits of detection for BoNT A2, A3, B2, and bivalent B using Endopep-MS.