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Sample records for plasma-mass spectrometry multi-elemental

  1. Use of dried blood spots and inductively coupled plasma mass spectrometry for multi-element determination in blood.

    PubMed

    Vacchina, Véronique; Huin, Vincent; Hulo, Sébastien; Cuny, Damien; Broly, Franck; Renom, Gilles; Perini, Jean-Marc

    2014-07-01

    The paper describes the development of an inductively coupled plasma mass spectrometry (ICP MS) method for multitrace element determination in dried blood spots (DBSs). The analytical conditions were optimized using Seronorm™ L-3 and L-1 Certified Reference Materials. The best results were obtained by sampling blood drops on a decontaminated PVDF filter membrane. After drying under metal-free conditions, the DBSs underwent acidic digestion and were analyzed with ICP MS. The method was then validated for As, Cd, Cu, Pb, Mo, Se and Zn. Using a matrix-matched calibration curve, the recovery levels ranged from 96% to 117%. The repeatability and reproducibility were generally below 15%. Limits of quantification ranging from 0.5 to 50 μg/L. In order to investigate the analytical procedure under real sampling conditions, the results obtained from DBSs and liquid blood aliquots (less subject to contamination) from two adult subjects were compared.

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

    USGS Publications Warehouse

    Wolf, Ruth E.; Adams, Monique

    2015-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2008-11-01

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

  4. Multi-elements (aluminium, copper, magnesium, manganese, selenium and zinc) determination in serum by dynamic reaction cell-inductively coupled plasma-mass spectrometry.

    PubMed

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

    2009-01-01

    Trace element determination in laboratory medicine is widely carried out by atomic absorption or emission spectroscopy. In the last decade, there has been a rapid growth in the use of inductively coupled plasma-mass spectrometry because of its strong detection power, and the possibility of multi-elements analysis in a single run. Having the advantages of smaller sample volume and better detection limit, we developed a method for the simultaneous determinations of six trace elements by using 100 microL serum, and the assay can be accomplished within 3 min. The method developed gave recovery of the six elements ranging from 97% to 117%. The method covered a wide dynamic range with manganese in the range of nmol/L, while magnesium was in the range of mmol/L. The detection limits were 0.001 mmol/L, 0.05 micromol/L, 2.0 nmol/L, 0.2 micromol/L, 0.05 micromol/L, and 0.01 micromol/L for magnesium, aluminium, manganese, copper, zinc, and selenium, respectively. All the six elements had intra-assay imprecision of less than 5%, and inter-assay imprecision of less than 8%. This fast and robust method is suitable for use in the clinical laboratory where short turnaround time is needed for managing patients with trace element deficiency or toxicity.

  5. Multi-element analysis using inductively coupled plasma mass spectrometry and inductively coupled plasma atomic emission spectroscopy for provenancing of animals at the continental scale.

    PubMed

    Kreitals, Natasha M; Watling, R John

    2014-11-01

    Chemical signatures within the environment vary between regions as a result of climatological, geochemical and anthropogenic influences. These variations are incorporated into the region's geology, soils, water and vegetation; ultimately making their way through the food chain to higher level organisms. Because the variation in chemical signatures between areas is significant, a specific knowledge of differences in elemental distribution patterns between, and within populations, could prove beneficial for provenancing animals or animal related products when applied to indigenous and feral faunal populations. The domestic pig (Sus scrofa domestica) was used as an investigative model to determine the feasibility of using a chemical traceability method for the provenance determination of animal tissue. Samples of pig muscle, tongue, stomach, heart, liver and kidney were collected from known farming areas around Australia. Samples were digested in 1:3 H2O2:HNO3 and their elemental composition determined using solution based Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Pigs from different growing regions in Australia could be distinguished based on the chemical signature of each individual tissue type. Discrimination was possible at a region, state and population level. This investigation demonstrates the potential for multi-element analysis of low genetic variation native and feral species of forensic relevance.

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

    PubMed

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

    2014-10-01

    This work explores the multi-element capabilities of inductively coupled plasma-mass spectrometry with collision/reaction cell technology (CCT-ICP-MS) for the simultaneous determination of both spectrally interfered and non-interfered nuclides in wine samples using a single set of experimental conditions. The influence of the cell gas type (i.e. He, He+H2 and He+NH3), cell gas flow rate and sample pre-treatment (i.e. water dilution or acid digestion) on the background-equivalent concentration (BEC) of several nuclides covering the mass range from 7 to 238u has been studied. Results obtained in this work show that, operating the collision/reaction cell with a compromise cell gas flow rate (i.e. 4 mL min(-1)) improves BEC values for interfered nuclides without a significant effect on the BECs for non-interfered nuclides, with the exception of the light elements Li and Be. Among the different cell gas mixtures tested, the use of He or He+H2 is preferred over He+NH3 because NH3 generates new spectral interferences. No significant influence of the sample pre-treatment methodology (i.e. dilution or digestion) on the multi-element capabilities of CCT-ICP-MS in the context of simultaneous analysis of interfered and non-interfered nuclides was observed. Nonetheless, sample dilution should be kept at minimum to ensure that light nuclides could be quantified in wine. Finally, a direct 5-fold aqueous dilution is recommended for the simultaneous trace and ultra-trace determination of spectrally interfered and non-interfered elements in wine by means of CCT-ICP-MS. The use of the CCT is mandatory for interference-free ultra-trace determination of Ti and Cr. Only Be could not be determined when using the CCT due to a deteriorated limit of detection when compared to conventional ICP-MS. Copyright © 2014 Elsevier B.V. All rights reserved.

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

    PubMed

    Spada, Nicholas; Bozlaker, Ayse; Chellam, Shankararaman

    2012-07-20

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

  8. Quantitative aspects of inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Bulska, Ewa; Wagner, Barbara

    2016-10-01

    Accurate determination of elements in various kinds of samples is essential for many areas, including environmental science, medicine, as well as industry. Inductively coupled plasma mass spectrometry (ICP-MS) is a powerful tool enabling multi-elemental analysis of numerous matrices with high sensitivity and good precision. Various calibration approaches can be used to perform accurate quantitative measurements by ICP-MS. They include the use of pure standards, matrix-matched standards, or relevant certified reference materials, assuring traceability of the reported results. This review critically evaluates the advantages and limitations of different calibration approaches, which are used in quantitative analyses by ICP-MS. Examples of such analyses are provided. This article is part of the themed issue 'Quantitative mass spectrometry'.

  9. Quantitative aspects of inductively coupled plasma mass spectrometry.

    PubMed

    Bulska, Ewa; Wagner, Barbara

    2016-10-28

    Accurate determination of elements in various kinds of samples is essential for many areas, including environmental science, medicine, as well as industry. Inductively coupled plasma mass spectrometry (ICP-MS) is a powerful tool enabling multi-elemental analysis of numerous matrices with high sensitivity and good precision. Various calibration approaches can be used to perform accurate quantitative measurements by ICP-MS. They include the use of pure standards, matrix-matched standards, or relevant certified reference materials, assuring traceability of the reported results. This review critically evaluates the advantages and limitations of different calibration approaches, which are used in quantitative analyses by ICP-MS. Examples of such analyses are provided.This article is part of the themed issue 'Quantitative mass spectrometry'.

  10. Laser Ablation Inductively Coupled Plasma Mass Spectrometry

    PubMed Central

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

    2015-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

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

    PubMed Central

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

    2014-01-01

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

  13. Ion sampling and transport in Inductively Coupled Plasma Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Farnsworth, Paul B.; Spencer, Ross L.

    2017-08-01

    Quantitative accuracy and high sensitivity in inductively coupled plasma mass spectrometry (ICP-MS) depend on consistent and efficient extraction and transport of analyte ions from an inductively coupled plasma to a mass analyzer, where they are sorted and detected. In this review we examine the fundamental physical processes that control ion sampling and transport in ICP-MS and compare the results of theory and computerized models with experimental efforts to characterize the flow of ions through plasma mass spectrometers' vacuum interfaces. We trace the flow of ions from their generation in the plasma, into the sampling cone, through the supersonic expansion in the first vacuum stage, through the skimmer, and into the ion optics that deliver the ions to the mass analyzer. At each stage we consider idealized behavior and departures from ideal behavior that affect the performance of ICP-MS as an analytical tool.

  14. [Study on the determination of 14 inorganic elements in coffee by inductively coupled plasma mass spectrometry].

    PubMed

    Nie, Xi-Du; Fu, Liang

    2013-07-01

    Samples of coffee were digested by microwave digestion, and inorganic elements amounts of Na, Mg, P, Ca, Cr, Mn, Fe, Co, Cu, Zn, As, Se, Mo and Pb in sample solutions were determined by inductively coupled plasma mass spectrometry (ICP-MS). HNO3 + H2O2 was used to achieve the complete decomposition of the organic matrix in a closed-vessel microwave oven. The working parameters of the instrument were optimized. The results showed that the relative standard deviation (RSD) was less than 3.84% for all the elements, and the recovery was found to be 92.00% -106.52% by adding standard recovery experiment. This method was simple, sensitive and precise and can perform simultaneous multi-elements determination of coffee, which could satisfy the sample examination request and provide scientific rationale for determining inorganic elements of coffee.

  15. [Study on the determination of trace elements in bitter almond by inductively coupled plasma mass spectrometry].

    PubMed

    Liu, Hong-Wei; Xie, Hua-Lin; Nie, Xi-Du

    2013-05-01

    Samples of bitter almond were digested by microwave digestion, and trace elements amounts of B, Na, Mg, Al, P, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Mo, Cd, Ba and Pb in sample solutions were determined by inductively coupled plasma mass spectrometry (ICP-MS). HNO3 + H2O2 was used to achieve the complete decomposition of the organic matrix in a closed-vessel microwave oven. The working parameters of the instrument were optimized. The result showed that the relative standard deviation (RSD) was less than 4.79% for all the elements, and the recovery was 90.00%-109.30% by adding standard recovery experiment. This method was simple, sensitive and precise and can perform simultaneo multi-elements determination for bitter almond, which could satisfy the sample examination request and provide scientific rationale for determining inorganic elements in bitter almond.

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

    PubMed

    Kokot, Zenon J; Matysiak, Jan

    2008-11-04

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

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

    NASA Astrophysics Data System (ADS)

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

    1994-02-01

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

  18. Environmental analysis by inductively coupled plasma mass spectrometry.

    PubMed

    Beauchemin, Diane

    2010-01-01

    This article reviews the numerous ways in which inductively coupled plasma mass spectrometry has been used for the analysis of environmental samples since it was commercially introduced in 1983. Its multielemental isotopic capability, high sensitivity and wide linear dynamic range makes it ideally suited for environmental analysis. Provided that some care is taken during sample preparation and that appropriate calibration strategies are used to circumvent non-spectroscopic interferences, the technique is readily applicable to the analysis of a wide variety of environmental samples (natural waters, soils, rocks, sediments, vegetation, etc.), using quadrupole, time-of-flight or double-focusing sector-field mass spectrometers. In cases where spectroscopic interferences arising from the sample matrix cannot be resolved, then separation methods can be implemented either on- or off-line, which can simultaneously allow analyte preconcentration, thus further decreasing the already low detection limits that are achievable. In most cases, the blank, prepared by following the same steps as for the sample but without the sample, limits the ultimate detection limits that can be reached.

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

    USGS Publications Warehouse

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

    2013-01-01

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

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

    PubMed

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

    2013-01-01

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

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

    PubMed

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

    2015-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-01-01

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

  3. Inductively Coupled Plasma-Mass Spectrometry and the European Discovery of America

    NASA Astrophysics Data System (ADS)

    Houk, R. S.

    2000-05-01

    The background and initial experimental results in inductively coupled plasma-mass spectrometry (ICP-MS) are juxtaposed with similar events from the voyages of Christopher Columbus, particularly with the first voyage.

  4. Inductively Coupled Plasma Mass Spectrometry and the Determination of Neptunium and Plutonium in the Marine Environment

    NASA Astrophysics Data System (ADS)

    Sampson, Kate

    This project is concerned with the application of inductively coupled plasma mass spectrometry (ICP-MS) to the determination of neptunium-237, plutonium-239 and plutonium-240 concentrations in the marine environment…

  5. The effect of pre-evaporation on ion distributions in inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Liu, Shulan; Beauchemin, Diane

    2006-02-01

    The connecting tube (2 or 5-mm i. d., 11-cm long) between the spray chamber and the torch was heated (to 400 °C) to investigate the effect of pre-evaporation on the distribution of ions in inductively coupled plasma mass spectrometry (ICP-MS). Axial and radial profiles of analyte ions (Al +, V +, Cr +, Ni +, Zn +, Mn +, Zn +, As +, Se +, Mo +, Cd +, Sb +, La +, Pb +) in 1% HNO 3 as well as some polyatomic ions (LaO +, ArO +, ArN +, CO 2+) were simultaneously obtained on a time-of-flight ICP-MS instrument. Upon heating the connecting tube, the optimal axial position of all elements shifted closer to the load coil. Without the heated tube, 3.5 mm was the compromise axial position for multielemental analysis, which was optimal for 6 analytes. With the heated tube, this position became 1.5 mm, which was then optimal for 9 of the 14 analytes. Furthermore, the radial profiles, which were wide with a plateau in their middle without heating, became significantly narrower and Gaussian-like with a heated tube. This narrowing, which was most important for the 5-mm tube, slightly (by a factor of two at the most) yet significantly (at the 95% confidence level) improved the sensitivity of all elements but Mn upon optimisation of the axial position for compromise multi-element analysis. Furthermore, a concurrent decrease in the standard deviation of the blank was significant at the 95% confidence level for 9 of the 14 analytes. For most of the analytes, this translated into a two-fold to up to an order of magnitude improvement in detection limit, which is commensurate with a reduction of noise resulting from the smaller droplets entering the plasma after traversing the pre-evaporation tube.

  6. Inductively Coupled Plasma Mass Spectrometry Uranium Error Propagation

    SciTech Connect

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

    2001-07-01

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

  7. 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

  8. Aerosol detection efficiency in inductively coupled plasma mass spectrometry

    SciTech Connect

    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 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

  9. 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

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

    NASA Technical Reports Server (NTRS)

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

    1999-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2005-11-01

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

  12. Elemental fingerprint analysis of barley (Hordeum vulgare) using inductively coupled plasma mass spectrometry, isotope-ratio mass spectrometry, and multivariate statistics.

    PubMed

    Husted, Søren; Mikkelsen, Birgitte F; Jensen, Jacob; Nielsen, Niels Erik

    2004-01-01

    Inductively coupled plasma mass spectrometry (ICP-MS) and isotope-ratio mass spectrometry (IR-MS) have been used to examine the multi-elemental composition and (15)N/(14)N and (13)C/(12)C isotope ratios of three spring barley (Hordeum vulgare) genotypes (Orthega, Barke, and Bartok) grown in three typical Danish agricultural soils (North Jutland, West Jutland, and East Zealand) differing in soil fertility. The aim of the study was to examine whether it was possible to generate a unique elemental fingerprint of individual barley genotypes irrespective of the elemental imprint plants had received from soils differing in fertility and agricultural practice. Multivariate statistics were used to analyze the elemental fingerprints of the barley genotypes at different times during a full growing season from early tillering to full maturity of the barley grains. Initially, 36 elements were analyzed in the plant samples but this number was subsequently reduced to 15 elements: B, Ba, C, Ca, Cu, Fe, K, Mg, Mn, N, Na, P, S, Sr, and Zn. These elements exceeded the limit of detection ( LOD) for all genotypes, soil types, and plant growth stages and for these elements the accuracy was better than 90% compared with apple leaf certified reference material (CRM). Principal component analysis (PCA) separated multi-elemental data in accordance with soil type when plants of similar physiological age were compared, whereas this separation disappeared if plants of all ages were compared simultaneously. Isotope ratios (delta(15)N) of plants also proved to be a highly accurate property for classification of samples according to soil type. In contrast, the differences in delta(13)C were too small to enable such classification. The differences in delta(15)N among soils were so pronounced that separation of samples according to the physiological age of plants became redundant. However, delta(15)N and the multi-elemental analysis revealed no differences between the three barley genotypes

  13. [Selenium determination in plasma/serum by inductively coupled plasma mass spectrometry (ICP-MS): comparison with graphite furnace atomic absorption spectrometry (GF-AAS)].

    PubMed

    Janasik, Beata; Trzcinka-Ochocka, Małgorzata; Brodzka, Renata

    2011-01-01

    The present study was aimed at comparing two techniques of selenium (Se) determination in serum/plasma samples: inductively coupled plasma mass spectrometry (ICP-MS) and graphite furnace atomic absorption (GF-AAS). Blood samples were collected by venipuncture, using Venosafe closed blood sampling system. The samples were centrifuged. The measurements were performed by Elan DRC-e mass spectrometry, Perkin Elmer, SCIEX, USA and Unicam Solar 989 QZ atomic absorption spectrometry. Reference material, Clincheck Serum Control Level 1 (Recipe, Germany), was used to verify the determinations. The Laboratory participates in external quality control (G-EQUAS). Analytical parameters for both techniques are respectively: ICP-MS--precision 5.9%, limit of detection 0.19 microg/l, repeatability 5.5%, trueness 2.4%, bias 97.6%, GF-AAS--precision 8%, limit of detection 3.4 microg/l, repeatability 7.2%, trueness 6.8%, bias 93.2%. The benefits of the ICP-MS technique are high accuracy, low detection limits and the possibility of multi-element analysis.

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

    USGS Publications Warehouse

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

    2014-01-01

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

  15. Quantitative bioanalysis of strontium in human serum by inductively coupled plasma-mass spectrometry

    PubMed Central

    Somarouthu, Srikanth; Ohh, Jayoung; Shaked, Jonathan; Cunico, Robert L; Yakatan, Gerald; Corritori, Suzana; Tami, Joe; Foehr, Erik D

    2015-01-01

    Aim: A bioanalytical method using inductively-coupled plasma-mass spectrometry to measure endogenous levels of strontium in human serum was developed and validated. Results & methodology: This article details the experimental procedures used for the method development and validation thus demonstrating the application of the inductively-coupled plasma-mass spectrometry method for quantification of strontium in human serum samples. The assay was validated for specificity, linearity, accuracy, precision, recovery and stability. Significant endogenous levels of strontium are present in human serum samples ranging from 19 to 96 ng/ml with a mean of 34.6 ± 15.2 ng/ml (SD). Discussion & conclusion: Calibration procedures and sample pretreatment were simplified for high throughput analysis. The validation demonstrates that the method was sensitive, selective for quantification of strontium (88Sr) and is suitable for routine clinical testing of strontium in human serum samples. PMID:28031925

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

    SciTech Connect

    Ihsanullah; East, B.W.

    1993-12-31

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

  17. Low-resolution continuum source simultaneous multi-element electrothermal atomic absorption spectrometry: steps into practice

    NASA Astrophysics Data System (ADS)

    Katskov, Dmitri

    2015-03-01

    The theory and practical problems of continuum source simultaneous multi-element electrothermal atomic absorption spectrometry (SMET AAS) are discussed by the example of direct analysis of underground water. The experimental methodology is based on pulse vaporization of the sample in a fast heated graphite tube and measurement of transient absorption of continuum spectrum radiation from D2 and Xe lamps within 200-400 nm wavelengths range with a low resolution spectral instrument and linear charge-coupled device. The setup permits the acquisition of 200 spectra during 1 s atomization pulse. Respective data matrix absorbance vs wavelength/time is employed for the quantification of elements in the sample. The calculation algorithm developed includes broad band and continuum background correction, linearization of function absorbance vs. concentration of atomic vapor and integration of thus modified absorbance at the resonance lines of the elements to be determined. Practical application shows that the method can be employed for the direct simultaneous determination of about 20 elements above microgram per liter level within 3-5 orders of the magnitude concentration range. The investigated sources of measurement errors are mainly associated with the atomization and vapor transportation problems, which are aggravated for the simultaneous release of major and minor sample constituents. Respective corrections concerning the selection of analytical lines, optimal sampling volume, matrix modification and cleaning of the atomizer have been introduced in the SMET AAS analytical technology. Under the optimized experimental conditions the calibration curves in Log-Log coordinates for all the investigated analytes in the single or multi-element reference solutions are approximated by the first order equations. The use of these equations as permanent characteristics of the setup enables instant quantification of Al, Ca, Co, Cr, Cu, Fe, Mg, Mn and Ni in the underground water

  18. EPA Method 200.8: Determination of Trace Elements in Waters and Wastes by Inductively Coupled Plasma-Mass Spectrometry

    EPA Pesticide Factsheets

    SAM lists this method for preparation and analysis of aqueous liquid and drinking water samples. This method will determine metal-containing compounds only as the total metal (e.g., total arsenic), inductively coupled plasma-mass spectrometry.

  19. Bioimaging of metals in brain tissue from micrometre to nanometre scale by laser ablation inductively coupled plasma mass spectrometry: State of the art and perspectives

    NASA Astrophysics Data System (ADS)

    Becker, J. Sabine

    2010-01-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) with multi-element capability is well established for the trace and ultratrace analysis of metals, metalloids and selected non-metals (such as C, P, S) in biological and clinical samples. Nowadays LA-ICP-MS is employed as a sensitive elemental mass spectrometric technique for the imaging of metals and non-metals in microtome thin tissue sections, especially for the determination of element concentrations at the trace and ultratrace level in selected small brain regions. This article discusses the state of the art of bioimaging of metals in thin brain tissue sections by LA-ICP-MS with spatial resolution at the micrometre scale and prospects for developing quantitative techniques at nanometre range.

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

    SciTech Connect

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

    1988-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-10-01

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

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

    PubMed

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

    2009-08-15

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

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

    PubMed

    Seltzer, Michael D

    2003-09-01

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

  4. Multiplex bio-assay with inductively coupled plasma mass spectrometry: Towards a massively multivariate single-cell technology

    NASA Astrophysics Data System (ADS)

    Tanner, Scott D.; Ornatsky, Olga; Bandura, Dmitry R.; Baranov, Vladimir I.

    2007-03-01

    Recent progress in the development of massively multiplexed bioanalytical assays using element tags with inductively coupled plasma mass spectrometry detection is reviewed. Feasibility results using commercially available secondary immunolabeling reagents for leukemic cell lines are presented. Multiplex analysis of higher order is shown with first generation tag reagents based on functionalized carriers that bind lanthanide ions. DNA quantification using metallointercalation allows for cell enumeration or mitotic state differentiation. In situ hybridization permits the determination of cellular RNA. The results provide a feasibility basis for the development of a multivariate assay tool for individual cell analysis based on inductively coupled plasma mass spectrometry in a cytometer configuration.

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

    USGS Publications Warehouse

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

    1987-01-01

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

  6. Radionuclide detection by inductively coupled plasma mass spectrometry: A comparison of atomic and radiation detection method

    SciTech Connect

    Smith, M.R.; Wyse, E.J.; Koppenaal, D.W.

    1991-04-01

    Radionuclide detection by mass spectrometric techniques offers inherent advantages over conventional radiation detection methods. Since radionuclides decay at variable rates (half-lives) and via various nuclear transformations (i.e. emission of alpha, beta, and/or gamma radiation) their determination via radiation detection depends not only on decay systematics but also on detector technology. Radionuclide detection by direct atom measurement, however, is dependent only on technique sensitivity and is indifferent to decay mode. Evaluation of inductively coupled plasma mass spectrometry (ICP/MS) indicates this method to be superior conventional radiation detection techniques for many radionuclides. This work discusses factors which influence detection by both methods. Illustrative applications of ICP/MS to the ultra-trace determination of several radionuclides, including {sup 129}I, are presented. 20 refs., 6 figs., 1 tab.

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

    USGS Publications Warehouse

    Lichte, F.E.

    1995-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1997-06-01

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

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

    USGS Publications Warehouse

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

    1988-01-01

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

  10. Development of analytical methods for multiplex bio-assay with inductively coupled plasma mass spectrometry.

    PubMed

    Ornatsky, Olga I; Kinach, Robert; Bandura, Dmitry R; Lou, Xudong; Tanner, Scott D; Baranov, Vladimir I; Nitz, Mark; Winnik, Mitchell A

    2008-01-01

    Advances in the development of highly multiplexed bio-analytical assays with inductively coupled plasma mass spectrometry (ICP-MS) detection are discussed. Use of novel reagents specifically designed for immunological methods utilizing elemental analysis is presented. The major steps of method development, including selection of elements for tags, validation of tagged reagents, and examples of multiplexed assays, are considered in detail. The paper further describes experimental protocols for elemental tagging of antibodies, immunostaining of live and fixed human leukemia cells, and preparation of samples for ICP-MS analysis. Quantitative analysis of surface antigens on model cell lines using a cocktail of seven lanthanide labeled antibodies demonstrated high specificity and concordance with conventional immunophenotyping.

  11. Development of analytical methods for multiplex bio-assay with inductively coupled plasma mass spectrometry

    PubMed Central

    Ornatsky, Olga I.; Kinach, Robert; Bandura, Dmitry R.; Lou, Xudong; Tanner, Scott D.; Baranov, Vladimir I.; Nitz, Mark; Winnik, Mitchell A.

    2008-01-01

    Advances in the development of highly multiplexed bio-analytical assays with inductively coupled plasma mass spectrometry (ICP-MS) detection are discussed. Use of novel reagents specifically designed for immunological methods utilizing elemental analysis is presented. The major steps of method development, including selection of elements for tags, validation of tagged reagents, and examples of multiplexed assays, are considered in detail. The paper further describes experimental protocols for elemental tagging of antibodies, immunostaining of live and fixed human leukemia cells, and preparation of samples for ICP-MS analysis. Quantitative analysis of surface antigens on model cell lines using a cocktail of seven lanthanide labeled antibodies demonstrated high specificity and concordance with conventional immunophenotyping. PMID:19122859

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

    NASA Astrophysics Data System (ADS)

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

    2008-05-01

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

  13. Analysis of iodine in food samples by inductively coupled plasma-mass spectrometry.

    PubMed

    Todorov, Todor I; Gray, Patrick J

    2016-01-01

    This work shows a method for the determination of iodine in a variety of food samples and reference materials using inductively coupled plasma-mass spectrometry (ICP-MS) following alkaline extraction. Optimisation of the addition of organic carbon showed that a minimum of 3% 2-propanol was necessary for a constant ratio of iodine to internal standard. The limit of quantification (LOQ), calculated as 30σ for the method, was 36 ng g(-1) in solid food samples. For method validation, seven standard reference materials (SRM) and 21 fortified food samples were used. The precision (%RSD) of the measurements was in the 2-7% range. Accuracies for the SRMs were 85-105%, while the fortified food samples showed 81-119% recoveries, including a number of samples fortified at 50% of the LOQ.

  14. Laser Ablation Inductively Coupled Plasma Mass Spectrometry: An Emerging Technology for Multiparametric Analysis of Tissue Antigens.

    PubMed

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

    2015-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  16. Analysis of biological reference materials, prepared by microwave dissolution, using inductively coupled plasma mass spectrometry.

    PubMed

    Friel, J K; Skinner, C S; Jackson, S E; Longerich, H P

    1990-03-01

    A procedure has been developed for the analysis of biological materials by inductively coupled plasma mass spectrometry (ICP-MS). Fast, efficient and complete sample digestion is achieved by a combined microwave-nitric acid/open beaker-nitric acid-hydrogen peroxide procedure. The ICP-MS analysis is performed with an on-line five-element internal standard to correct for matrix and instrumental drift effects. Results are presented for 24 elements in three biological reference materials (National Institute of Standards and Technology Standard Reference Materials 5277a Liver and 1566 Oyster and International Atomic Energy Agency Certified Reference Material H4 Animal Muscle). For all elements significantly above the detection limit and reagent blank concentrations, good agreement exists between ICP-MS and certified values.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  18. Plutonium bioassay by inductively coupled plasma mass spectrometry ICP/MS

    SciTech Connect

    Wyse, E.J.; Fisher, D.R.

    1993-04-01

    The determination of plutonium in urine poses several analytical challenges, e.g., detectability, matrix, etc. We have investigated the feasibility of analyzing plutonium in processed urine by inductively coupled plasma mass spectrometry (ICP/MS). The urine samples are first spiked with [sup 244]Pu as a tracer and internal standard, then processed by co-precipitation and column chromatography using TRU-Spec[trademark], an extraction resin. By enhancing ICP/MS detection capabilities via improved sample introduction and data acquisition efficiencies, an instrumental detection limit of 5 to 50 fg (0.3 to 3 fCi for [sup 239]pu) is typically obtained, depending on the desired degree of quantitation. A brief summary of the analytical method as well as the basis for measuring radionuclides by ICP/MS are submitted; the separation procedure, methods of sample introduction, and data acquisition techniques are then highlighted.

  19. Plutonium bioassay by inductively coupled plasma mass spectrometry ICP/MS

    SciTech Connect

    Wyse, E.J.; Fisher, D.R.

    1993-04-01

    The determination of plutonium in urine poses several analytical challenges, e.g., detectability, matrix, etc. We have investigated the feasibility of analyzing plutonium in processed urine by inductively coupled plasma mass spectrometry (ICP/MS). The urine samples are first spiked with {sup 244}Pu as a tracer and internal standard, then processed by co-precipitation and column chromatography using TRU-Spec{trademark}, an extraction resin. By enhancing ICP/MS detection capabilities via improved sample introduction and data acquisition efficiencies, an instrumental detection limit of 5 to 50 fg (0.3 to 3 fCi for {sup 239}pu) is typically obtained, depending on the desired degree of quantitation. A brief summary of the analytical method as well as the basis for measuring radionuclides by ICP/MS are submitted; the separation procedure, methods of sample introduction, and data acquisition techniques are then highlighted.

  20. Determination of metals in composite diet samples by inductively coupled plasma-mass spectrometry.

    PubMed

    Melnyk, Lisa Jo; Morgan, Jeffrey N; Fernando, Reshan; Pellizzari, Edo D; Akinbo, Olujide

    2003-01-01

    A study was conducted to evaluate the applicability of inductively coupled plasma-mass spectrometry (ICP-MS) techniques for determination of metals in composite diets. Aluminum, cadmium, chromium, copper, lead, manganese, nickel, vanadium, and zinc were determined by this method. Atmospheric pressure microwave digestion was used to solubilize analytes in homogenized composite diet samples, and this procedure was followed by ICP-MS analysis. Recovery of certified elements from standard reference materials ranged from 92 to 119% with relative standard deviations (RSDs) of 0.4-1.9%. Recovery of elements from fortified composite diet samples ranged from 75 to 129% with RSDs of 0-11.3%. Limits of detection ranged from 1 to 1700 ng/g; high values were due to significant amounts of certain elements naturally present in composite diets. Results of this study demonstrate that low-resolution quadrupole-based ICP-MS provides precise and accurate measurements of the elements tested in composite diet samples.

  1. Authenticity of Benin metalworks evaluated by inductively coupled plasma mass spectrometry and lead isotope analyses

    NASA Astrophysics Data System (ADS)

    Fabbri, E.; Soffritti, C.; Merlin, M.; Vaccaro, C.; Garagnani, G. L.

    2017-05-01

    Two metal plaques and a cock statuette belonging to a private collection and stylistically consistent with the Royal Art of Benin (Nigeria) were investigated in order to verify their authenticity. The characterization of alloys and patinas were carried out by inductively coupled plasma mass spectrometry, optical microscopy, scanning electron microscopy and energy dispersion spectroscopy, and X-Ray diffraction spectrometry. Furthermore, thermal ionization mass spectrometry was used to assess the abundances of lead isotopes and to attempt a dating by the measurement of 210Pb/204Pb ratio. The results showed that all three artefacts were mainly composed of low lead-brass alloys, with relatively high concentrations of zinc, antimony, cadmium and aluminum in the solid copper solution. Microstructures were mostly dendritic, typical of as-cast brasses, and characterized by recrystallized non-homogeneous twinned grains in areas corresponding to surface decorations, probably due to multiple hammering steps followed by partial annealing treatments. The matrix was composed of a cored α-Cu solid solution together with non-metallic inclusions, lead globules and Sn-rich precipitates in interdendritic spaces. On the surface of all metalworks, both copper and zinc oxides, a non-continuous layer of sulphur-containing contaminants and chloride-containing compounds, were identified. The lead isotope results were consistent with brasses produced shortly before or after 1900 CE. Overall, the data obtained by different techniques supported the hypothesis that the three artefacts were not authentic.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

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

    PubMed

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

    2007-06-01

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

  4. Isotope ratio analysis of individual sub-micrometer plutonium particles with inductively coupled plasma mass spectrometry.

    PubMed

    Esaka, Fumitaka; Magara, Masaaki; Suzuki, Daisuke; Miyamoto, Yutaka; Lee, Chi-Gyu; Kimura, Takaumi

    2010-12-15

    Information on plutonium isotope ratios in individual particles is of great importance for nuclear safeguards, nuclear forensics and so on. Although secondary ion mass spectrometry (SIMS) is successfully utilized for the analysis of individual uranium particles, the isobaric interference of americium-241 to plutonium-241 makes difficult to obtain accurate isotope ratios in individual plutonium particles. In the present work, an analytical technique by a combination of chemical separation and inductively coupled plasma mass spectrometry (ICP-MS) is developed and applied to isotope ratio analysis of individual sub-micrometer plutonium particles. The ICP-MS results for individual plutonium particles prepared from a standard reference material (NBL SRM-947) indicate that the use of a desolvation system for sample introduction improves the precision of isotope ratios. In addition, the accuracy of the (241)Pu/(239)Pu isotope ratio is much improved, owing to the chemical separation of plutonium and americium. In conclusion, the performance of the proposed ICP-MS technique is sufficient for the analysis of individual plutonium particles.

  5. Speciation of chromium in waste water using ion chromatography inductively coupled plasma mass spectrometry.

    PubMed

    Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravendra

    2007-04-30

    Ion chromatography (IC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) was systematically investigated for determining the speciation of chromium in environmental samples. Firstly, the stability of complexes formed by Cr(III) with various aminopolycarboxylic acids was studied by electrospray ionization mass spectrometry (ESI-MS). The results showed that [Cr(EDTA)](-) was stable in solution. Secondly, various mobile phases were examined to separate Cl(-) from chromium species by IC to avoid Cl(-) interference. The separation of [Cr(EDTA)](-) and Cr(VI) was achieved on a new anion-exchange column (G3154A/102) using a mobile phase containing 20mM NH(4)NO(3) and 10mM NH(4)H(2)PO(4) at pH 7.0 without Cl(-) interference. Detection limits for chromium species were below 0.2 microg/L with a direct injection of sample and without prior removal of interferences from the matrix. Finally, the proposed method was used for the determination of chromium species in contaminated waters.

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

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

    NASA Astrophysics Data System (ADS)

    Yang, Karl X.; Swami, Kamal

    2007-10-01

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

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

    PubMed

    Nie, Xi-du; Fu, Liang

    2015-11-01

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

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

    PubMed

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

    2016-02-01

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

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

    SciTech Connect

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

    2010-06-23

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

  11. [Determination of 24 minerals in human milk by inductively coupled plasma mass spectrometry with microwave digestion].

    PubMed

    Sun, Zhongqing; Yue, Bing; Yang, Zhenyu; Li, Xiaowei; Wu, Yongning; Yin, Shian

    2013-05-01

    To determine the levels of 24 minerals in human milk by inductively coupled plasma mass spectrometry with microwave digestion. The samples were digested by microwave. The contents of minerals were determined by inductively coupled plasma mass spectrometry. The standard reference minerals of 1849a and 1568a from National Institute of Science and Technology were used for quality control. The accuracy and reproduability for this method were evaluated with mix standards and 1849a and 1568a standard reference materials. The ranges of the levels of sodium, magnesium, phosphorus, potassium, calcium, aluminum, chromium, arsenic, selenium, iron, zinc, manganese, copper, molybdenum, vanadium, cobalt, nickel, gallium, cadmium, silver, strontium, cesium, barium, lead in human milk was 34.97-415.83 mg/kg, 19.00-39.52 mg/kg, 102.13-274.53 mg/kg, 351.19-713.99 mg/kg, 180.08-349.64 mg/kg, 0.06-0.44 mg/kg, 0.9-7.37 microg/kg, 0.92-2.72 microg/kg, 0.20-21.15 microg/kg, 0.10-0.70 mg/kg, 0.56-3.25 mg/kg, 3.00-16.12 micro.g/kg, 62.16-591.69 microg/kg, 0.02-6.91 microg/kg, 5.99-13.70 microg/kg, 0.07-2.11 microg/kg, 0.77-209.26 microg/kg, 0.005-0.28 microg/kg, 0.02-0.23 microg/kg, 0.02-0.71 microg/kg, 36.89-132.26 microg/kg, 0.01-4.72 microg/kg, 0.83-28.16 microg/kg, 2.5-5.3 microg/kg, respectively. The levels of minerals in human milk in present study were consisted with other similar studies. The experiment examined the levels of minerals in human milk satisfactorily. The method has high accuracy and good reproducibility, which could be used for understanding the levels of minerals in human milk.

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

    NASA Astrophysics Data System (ADS)

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

    2000-12-01

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

  13. Determination of essential and toxic elements in Cordyceps kyushuensis Kawam by inductively coupled plasma mass spectrometry.

    PubMed

    Zhang, Guoying; Zhao, Yanxin; Liu, Fengjun; Ling, Jianya; Lin, Jianqiang; Zhang, Changkai

    2013-01-01

    In this study, a total of 20 elements (essential, non-essential and toxic): lithium (Li), sodium (Na), potassium (K), gallium (Ga), magnesium (Mg), zinc (Zn), iron (Fe), copper (Cu), manganese (Mn), vanadium (V), chromium (Cr), nickel (Ni), cobalt (Co), molybdenum (Mo), selenium (Se), barium (Ba), tin (Sn), arsenic (As), lead (Pb) cadmium (Cd) and mercury (Hg) in natural and cultured Cordyceps kyushuensis have been determined by means of inductively coupled plasma mass spectrometry (ICP-MS). Cultured stroma, natural stroma and natural worm were digested by microwave-assisted method before analysis. The proposed ICP-MS method was validated by analyzing a certified reference material (CRM) GBW10015 (spinach). The results of one-way analysis of variance (ANOVA) revealed that the element concentrations in the three kinds of samples were significantly different (p<0.05). Except for Mg, Zn, Cu, the values of other elemental contents were the highest in the stroma of natural C. kyushuensis. In comparison with the worm, the concentrations of determined elements in wild stroma were higher. The remarkable difference of elemental contents between cultured and natural stroma may be caused by distinct growing environment. This finding highlighted the usefulness of ICP-MS elemental analysis and enhanced the value of C. kyushuensis as a candidate for nourishing food based on its composition. Copyright © 2012 Elsevier B.V. All rights reserved.

  14. Determination of total iodine in foods and dietary supplements using inductively coupled plasma-mass spectrometry.

    PubMed

    Sullivan, Darryl; Zywicki, Richard

    2012-01-01

    A method was developed and validated for the determination of total iodine in a wide variety of food products and dietary supplements. The method involves a unique sample digestion with a KOH solution in an oven or by using an open-vessel microwave system. After digestion, a stabilizer is added and the solution is taken to volume, then filtered and analyzed either directly or after dilution. The amount of iodine is determined with inductively coupled plasma-mass spectrometry (ICP-MS). The method was validated by experiments to determine its precision, accuracy, linearity, specificity, ruggedness, and robustness. The LOQ of this method is 25-50 microg/kg. The method demonstrated an average RSD of 2.27% during analysis of milk powder and 4.30% during analysis of a dietary supplement tablet reference material. The accuracy of the method as determined with these same reference materials was 100 and 94.2%, respectively. The method has been used successfully on commodity foods, processed foods, dairy products, pet food, infant formula, animal feed, mineral premixes, and a variety of dietary supplements.

  15. An improved candidate reference method for serum potassium measurement by inductively coupled plasma-mass spectrometry.

    PubMed

    Zhang, Rui; Ma, Huaian; Li, Huiling; Xu, Jing; Zhang, Jianping; Zhang, Yang; Wang, Qingtao

    2013-05-01

    In 2002, the National Institute of Standards and Technology (NIST) established a reference method for serum potassium based on inductively coupled plasma-mass spectrometry (ICP-MS). The aim of this study was to develop an inexpensive and improved candidate reference method for accurate and precise determination of serum potassium. Serum samples were diluted with 1% HNO3 supplemented with (59)Cobalt as isotope internal standard, and potassium was measured by ICP-MS. The new method was evaluated with NIST standard reference materials (SRMs), according to the Clinical and Laboratory Standard Institute's evaluation protocols. At 4.300 and 4.678 mmol/l levels, the present method demonstrated analytical imprecision of 0.09% and 0.14%, and recoveries of 99.67% to 99.88%, respectively. The bias between the target values of SRMs were -0.02% to +0.28%, respectively. This method was linear between 0.0000 and 6.87 mmol/l (R(2)=1.000). The method had an uncertainty (U95%) of 0.76%. The proposed ICP-MS method to measure serum potassium is precise and accurate, with high sensitivity and specificity. It may be considered as a candidate reference method for the determination of serum potassium. Copyright © 2012 Elsevier B.V. All rights reserved.

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

    PubMed

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

    2016-05-01

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

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

    SciTech Connect

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

    1996-09-01

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

  18. Determination of platinum in human subcellular microsamples by inductively coupled plasma mass spectrometry.

    PubMed

    Björn, Erik; Nygren, Yvonne; Nguyen, Tam Trinh Thi Nhu; Ericson, Christer; Nöjd, Mikael; Naredi, Peter

    2007-04-01

    A fast and robust method for the determination of platinum in human subcellular microsamples by inductively coupled plasma mass spectrometry was developed, characterized, and validated. Samples of isolated DNA and exosome fractions from human ovarian (2008) and melanoma (T289) cancer cell lines were used. To keep the sample consumption to approximately 10 microl and obtain a high robustness of the system, a flow injection sample introduction system with a 4.6-microl sample loop was used in combination with a conventional pneumatic nebulizer and a spray chamber. The system was optimized with respect to signal/noise ratio using a multivariate experimental design. The system proved to be well suited for routine analysis of large sample series, and several hundreds of samples could be analyzed without maintenance or downtime. The detection limit of the method was 0.12 pg (26 pg/g) platinum. To avoid systematic errors from nonspectral interferences, it was necessary to use reagent matched calibration standards or isotope dilution analysis. An uncertainty budget was constructed to estimate the total expanded uncertainty of the method, giving a quantification limit of 2.3 pg (0.5 ng/g) platinum in DNA samples. The uncertainty was sufficiently low to study quantitative differences in the formation of Pt-DNA adducts after treatment with cisplatin using different exposure times and concentrations.

  19. 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.

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

    SciTech Connect

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

    1993-12-31

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

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

    USGS Publications Warehouse

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

    1987-01-01

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

  2. Arsenic speciation in soil using high performance liquid chromatography/inductively coupled plasma/mass spectrometry

    SciTech Connect

    Bass, D.A.; Yaeger, J.S.; Parish, K.J.; Crain, J.S.; Kiely, J.T.; Gowdy, M.J.; Mohrman, G.B.; Besmer, M.G.

    1996-08-01

    A method has been developed to identify and quantify As(III), As(V), and organoarsenic compounds in soil samples from the Rocky Mountain Arsenal (RMA) by high performance liquid chromatography/inductively coupled plasma/mass spectrometry (HPLC/ICP/MS). The soils were extracted using tetrabutylammonium hydroxide (TBAH) and sonication. The percentages of As(III), As(V), and organoarsenic species extracted from soil samples were 30, 50, and 100 respectively. The arsenic species were not altered during the extraction process. They were separated by reversed-phase, ion-pairing, HPLC using a microbore Inertsil-ODS{trademark} column. The HPLC column effluent was introduced into an ICP/MS system using a direct injection nebulizer (DIN). Detection limits of less than 1 pg were readily obtained for each arsenic species. Internal standards are recommended to increase accuracy and precision. Soil samples spiked with arsenic oxide, sodium arsenate, dimethylarsinic acid (DMAA), and chlorovinyl arsenious acid (CVAA) were extracted, identified and quantified with the HPLC/ICP/MS system. The soil samples were analyzed in support of the analytical needs of a thermal desorption treatability study being conducted at the RMA.

  3. Characterization of microconcentric nebulizer uptake rates for capillary electrophoresis inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

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

    2003-05-01

    There is demonstrated interest in combining capillary electrophoresis (CE) with inductively coupled plasma mass spectrometry (ICP-MS) for speciation determinations. When self-aspirating nebulizers are used for this application, it is important to offset the suction effect to avoid degradation of the separation. In this study, sample uptake rates for three microconcentric nebulizers of the same model, in combination with a cyclonic spray chamber, were characterized and compared for future utilization in CE-ICP-MS interfaces. The specific model studied was a MicroMist with a nominal uptake rate of 100 μl/min at 1 l/min argon gas flow rate per the manufacturer's specifications. Sample uptake rates at various nebulizer gas flows were measured by aspirating water from a weighed container and calculating the uptake rate in microliter per minute. The nebulizers studied provided good reproducibility from day to day, but a comparison of the different nebulizers reflected a significant difference in performance. A characteristic observed during the study was that uptake rates decreased with increasing nebulizer gas flow. This can be used for sample introduction for CE-ICP-MS. Interestingly, very different performance was observed when comparing the three different nebulizers of the same model. Uptake rates showed strong dependence on argon gas flow rates and the dimensions of the sample uptake tubing.

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

    PubMed

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

    2016-08-26

    We reported sensitivity enhancement using multichannel parallel separation for microchip electrophoresis hyphenated with inductively coupled plasma mass spectrometry (MCE-ICP-MS) in this study. By using 2-20 array lanes for parallel separation, the sensitivity of the MCE-ICP-MS system was proportionally improved by 2-20 folds. No significantly adverse effect of parallel separation on column efficiency and resolution was observed. Rapid separation of Hg(2+) and methylmercuric (MeHg) ion within 36s under an electric field of 800Vcm(-1) was achieved in the 2-cm twenty-channels with a background electrolyte of 5mmolL(-1) borate buffer (pH 9.2). Detection limits of Hg(2+) and MeHg by the proposed system were decreased to 6.8-7.1ngL(-1). Good agreement between determined values and certified values of a certified reference fish was obtained with recoveries ranged between 94-98%. All results prove its advantages including high sensitivity, high efficiency and low operation cost, which are beneficial to routine analysis of metal speciation in environmental, biological and food fields. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  6. Profiling metals in Cordyceps sinensis by using inductively coupled plasma mass spectrometry.

    PubMed

    Wei, Xin; Hu, Hankun; Zheng, Baogeng; Arslan, Zikri; Huang, Hung-Chung; Mao, Weidong; Liu, Yi-Ming

    2017-01-28

    Cordyceps sinensis (C. sinensis) is a natural product that has diverse nutritional and medicinal values. Since the availability of natural C. sinensis becomes limited its authentication and quality control is of high significance. Herein we report on profiling of metals in C. sinensis by using inductively coupled plasma mass spectrometry (ICP-MS). The analysis reveals that C. sinensis contains a wide array of essential elements, including P, Mg, Zn, Cu, Fe, etc. Toxic metals detected are Cd, Pb, and As. In all five samples analyzed Pb contents are below 2.0 ppm. Arsenic level in C. sinensis caterpillar is significantly higher than that in its mycelium and varies from 3.0 to 32 ppm likely due to soil contamination. It's for the first time demonstrated in this work that clustering analysis on the proposed metal profiles consisting of 24 elements is very useful to identify "abnormal" C. sinensis samples, thus adding another dimension to the effective means for authentication and quality assessment of this highly demanded previous natural product.

  7. Element fingerprinting of marine organisms by dynamic reaction cell inductively coupled plasma mass spectrometry.

    PubMed

    Cubadda, Francesco; Raggi, Andrea; Coni, Ettore

    2006-02-01

    A method for the determination of sixteen elements (Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Se, Sn, V, Zn) in seafood by dynamic reaction cell inductively coupled plasma mass spectrometry (ICP-DRC-MS) is presented. A preliminary study of polyatomic interferences was carried out in relation to the chemical composition of marine organisms belonging to different taxa. Acid effects and other matrix effects in marine organisms submitted to closed-vessel microwave digestion were investigated as well. Ammonia was the reactive gas used in the DRC to remove polyatomic ions interfering with 27Al, 52Cr, 56Fe and 51V. Optimal conditions for the simultaneous determination of analytes were identified in order to develop a fast multielement method. A suite of real samples (mussels and various fish species) were used during method development along with three certified reference materials: BCR CRM 278R (mussel tissue), BCR CRM 422 (cod muscle) and DORM-2 (dogfish muscle). The proposed analytical approach can be used in conjunction with suitable chemometric procedures to address quality and safety issues in aquaculture and fisheries. As an example, a case study is described in which mussels from three farming sites in the Venice Lagoon were distinguished by multivariate analysis of element fingerprints.

  8. Sensitive sandwich immunoassay based on single particle mode inductively coupled plasma mass spectrometry detection.

    PubMed

    Liu, Rui; Xing, Zhi; Lv, Yi; Zhang, Sichun; Zhang, Xinrong

    2010-11-15

    A sensitive sandwich type immunoassay has been proposed with the detection by inductively coupled plasma mass spectrometry (ICP-MS) in a single particle mode (time resolved analysis). The signal induced by the flash of ions ((197)Au(+)) due to the ionization of single Au-nanoparticle (Au-NP) label in the plasma torch can be measured by the mass spectrometer. The frequency of the transient signals is proportional to the concentration of Au-NPs labels. Characteristics of the signals obtained from Au-NPs of 20, 45 and 80 nm in diameters were discussed. The analytical figures for the determination of Au-labeled IgG using ICP-MS in conventional integral mode and single particle mode were compared in detail. Rabbit-anti-human IgG was used as a model analyte in the sandwich immunoassay. A detection limit (3 σ) of 0.1 ng mL(-1) was obtained for rabbit-anti-human IgG after immunoreactions, with a linear range of 0.3-10 ng mL(-1) and a RSD of 8.1% (2.0 ng mL(-1)). Finally, the proposed method was successfully applied to spiked rabbit-anti-human IgG samples and rabbit-anti-human serum samples. The method resulted to be a highly sensitive ICP-MS based sandwich type immunoassay.

  9. [Determination of blue ballpoint pen ink by laser ablation inductively coupled plasma mass spectrometry].

    PubMed

    Ma, Dong; Shen, Min; Luo, Yi-wen; Bo, Jun; Xu, Che; Zhuo, Xian-yi

    2010-10-01

    To establish an identification method for the forensic analysis of blue ballpoint ink by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), 95 kinds of blue ballpoint pen from different manufacturers were detected. These blue ballpoint pens were classified into 34 groups according to their metal element components, among which, 26 groups can be directly distinguished according to the types of metal element components contained in the ballpoint pen, the other groups can be distinguished by different element response ratios. Meanwhile the examination result on the papers showed that the papers have no impact on the ink handwriting analysis. Experimental results showed that the method's reproducibility is good and precision is less than 10%. This method has better identification ability than traditional identification technology for questioned document. Eighty eight kinds of blue ballpoint pen out of the total 95 selected kinds can be distinguished with this method. The established method is simple, rapid, with good precision, and almost has no damage to the sample. It is particularly suitable for the demand of identification of blue ballpoint pen in forensic science.

  10. Atomic Mineral Characteristics of Indonesian Osteoporosis by High-Resolution Inductively Coupled Plasma Mass Spectrometry

    PubMed Central

    Noor, Zairin; Sumitro, Sutiman Bambang; Hidayat, Mohammad; Rahim, Agus Hadian; Sabarudin, Akhmad; Umemura, Tomonari

    2012-01-01

    Clinical research indicates that negative calcium balance is associated with low bone mass, rapid bone loss, and high fracture rates. However, some studies revealed that not only calcium is involved in bone strengthening as risk factor of fracture osteoporosis. Thus, in this report, the difference of metallic and nonmetallic elements in osteoporosis and normal bones was studied by high-resolution inductively coupled plasma mass spectrometry (HR-ICP-MS). The influence of these elements on bone metabolic processes is also discussed. Inclusion criteria of bone samples consist of postmenopausal woman, trabecular bone fracture, normal and osteoporosis BMD value, and no history of previous disease. The results showed that the concentration of B, Al, S, V, Co, Mo, Te, Ba, La, Ni, As, and Ca/P ratio is higher in osteoporosis than normal. These atomic minerals have negative role to imbalance between bone resorption and bone formation activity. Conversely, concentrations of Na, Mg, P, K, Ca, Cr, Pd, Ag, Mn, Fe, Cu, Zn, Rb, Sr, Pb, and Se are lower in osteoporosis than in normal bones. Among these atoms, known to have important roles in bone structure, we found involvement of atomic mineral and calcium which are considerable to contribute to osteoporotic phenomena. PMID:22654598

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

    PubMed

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

    2001-06-01

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

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

    PubMed Central

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

    2015-01-01

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

  13. Cadmium measurements in coral skeleton using isotope dilution-inductively coupled plasma-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Matthews, Kathryn A.; McDonough, William F.; Grottoli, AndréA. G.

    2006-11-01

    Here a method for the precise analysis of Cd/Ca in coral skeleton using inductively coupled plasma-mass spectrometry (ICP-MS) is presented. Isotope dilution and gravimetric standards with internal standardization were used for Cd and Ca determination, respectively. Separation of alkaline earth metals from Cd using ion chromatography reduced the high total dissolved solids while maintaining a strong Cd signal. Repeated Cd/Ca measurements of a coral standard yielded a precision of ±2.2% (one standard deviation as a fraction of signal). Analyses of reference materials (BCR-1, BHVO-1, W-2, GSR-3, GSR-6, CACB-1, JCp-1, and JCt-1) fell within established ranges, with a precision comparable to other ICP-MS measurements. Advantages of this approach over existing methods for corals are as follows: (1) reduced introduction of high-concentration elements into the mass spectrometer, (2) sample requirements as low as 15 mg (i.e., ≥1 pmol Cd/sample), and (3) determination of multiple element ratios on the same sample aliquot with a precision of ±7% or better.

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

    SciTech Connect

    Bricker, Tonya

    1994-07-27

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

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

    PubMed

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

    2014-10-17

    Here we present a novel coupling of thin-layer chromatography (TLC) to diode laser thermal vaporization inductively coupled plasma mass spectrometry (DLTV ICP MS). DLTV is a new technique of aerosol generation which uses a diode laser to induce pyrolysis of a substrate. In this case the cellulose stationary phase on aluminum-backed TLC sheets overprinted with black ink to absorb laser light. The experimental arrangement relies on economic instrumentation: an 808-nm 1.2-W continuous-wave infrared diode laser attached to a syringe pump serving as the movable stage. Using a glass tubular cell, the entire length of a TLC separation channel is scanned. The 8-cm long lanes were scanned in ∼35 s. The TLC - DLTV ICP MS coupling is demonstrated on the separation of four cobalamins (hydroxo-; adenosyl-; cyano-; and methylcobalamin) with limits of detection ∼2 pg and repeatability ∼15% for each individual species. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Thorium colloid analysis by single particle inductively coupled plasma-mass spectrometry.

    PubMed

    Degueldre, C; Favarger, P-Y

    2004-04-19

    Thorium colloid analysis in water has been carried out by a single particle mode using inductively coupled plasma mass spectrometry (ICP-MS). The flash of ions due to the ionisation of a thorium colloidal particle in the plasma torch can be detected and measured in a time scan for (232)Th (+ ) or (248)[ThO] (+ ) according to the sensitivity required by the mass spectrometer. The peaks of the recorded intensity of the MS signal can be analysed as a function of the particle size or fraction of the studied element in the colloid phase. The frequency of the flashes is directly proportional to the concentration of particles in the colloidal suspension. After discussing Th colloid detection, on the basis of the intensity of the ion flashes generated in the plasma torch, tests were performed on thorium dioxide colloidal particles. This feasibility study also describes the experimental conditions and the limitation of the plasma design to detect thorium colloids in a single particle analysis mode down to about 10fg.

  17. Monitoring of platinum surface contamination in seven Dutch hospital pharmacies using inductively coupled plasma mass spectrometry

    PubMed Central

    Huitema, A. D. R.; Bakker, E. N.; Douma, J. W.; Schimmel, K. J. M.; van Weringh, G.; de Wolf, P. J.; Schellens, J. H. M.; Beijnen, J. H.

    2007-01-01

    Objective: To develop, validate, and apply a method for the determination of platinum contamination, originating from cisplatinum, oxaliplatinum, and carboplatinum. Methods: Inductively coupled plasma mass spectrometry (ICP-MS) was used to determine platinum in wipe samples. The sampling procedure and the analytical conditions were optimised and the assay was validated. The method was applied to measure surface contamination in seven Dutch hospital pharmacies. Results: The developed method allowed reproducible quantification of 0.50 ng l−1 platinum (5 pg/wipe sample). Recoveries for stainless steel and linoleum surfaces ranged between 50.4 and 81.4% for the different platinum compounds tested. Platinum contamination was reported in 88% of the wipe samples. Although a substantial variation in surface contamination of the pharmacies was noticed, in most pharmacies, the laminar-airflow (LAF) hoods, the floor in front of the LAF hoods, door handles, and handles of service hatches showed positive results. This demonstrates that contamination is spread throughout the preparation rooms. Conclusion: We developed and validated an ultra sensitive and reliable ICP-MS method for the determination of platinum in surface samples. Surface contamination with platinum was observed in all hospital pharmacies sampled. The interpretation of these results is, however, complicated. PMID:17377802

  18. Comparison of sample preservation methods for clinical trace element analysis by inductively coupled plasma mass spectrometry.

    PubMed

    Bornhorst, Joshua A; Hunt, John W; Urry, Francis M; McMillin, Gwen A

    2005-04-01

    The effects of chemical additives and storage temperatures on measurement of 16 trace elements in urine by inductively coupled plasma mass spectrometry (ICP-MS) were evaluated. A 24-hour urine specimen was supplemented with concentrations of the elements. Aliquots containing 1 of 4 chemical additives were stored at 3 different temperatures in sealed polypropylene containers. Elemental concentrations were determined by ICP-MS for the resulting samples after 1, 2, 8, and 65 days of storage. Initial element concentrations measured within 8 hours of specimen preparation were consistent with expected concentrations (except for aluminum). For most elements, preservation and storage conditions yielded consistent measured concentrations throughout the experiment. Notable exceptions were for aluminum (general rise over time) and mercury (general decrease over time). Adding boric acid and potassium pyrosulfate resulted in sample contamination; elemental contamination was concentration-dependent for both. Although little microbial contamination was observed during the experiment, refrigeration of samples is recommended to curtail bacterial growth in nonsterile specimens. In light of these results, refrigerated urine storage without the use of chemical additives is an effective preservation method for ICP-MS analysis of many trace elements.

  19. Determination of vanadium by reaction cell inductively coupled plasma mass spectrometry.

    PubMed

    Bednar, A J

    2009-04-30

    Recent advances in inductively coupled plasma mass spectrometry (ICP-MS) have included the addition of interference reduction technologies, such as collision and reaction cells, to improve its detection capability for certain elements that suffer from polyatomic interferences. The principle behind reaction cell (RC)-ICP-MS is to remove a particular polyatomic interference by dissociation or formation of a different polyatomic species that no longer interferes with the analyte of interest. However, some interferences cannot be removed by commonly reported reaction gases, such as hydrogen, oxygen, or methane, necessitating using more reactive and hazardous gases, such as ammonia. The current study investigates oxygen as a reaction gas in RC-ICP-MS to specifically react with vanadium analyte ions, rather than the interferents, to produce a polyatomic analyte species and thereby provide a way to analyze for vanadium in complex environmental matrices. The technique has been tested on a series of river water, tap water, and synthetic laboratory samples, and shown to be successful in vanadium analyses in high chloride and sulfate matrices. The zinc isobaric interference on the new vanadium oxide analyte at m/z 67 is also investigated, and can be corrected by using a standard mathematical correction equation. The results of this study further increase the utility of RC-ICP-MS analytical techniques for complex environmental matrices.

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

    PubMed

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

    2015-04-01

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

  1. [Determination of arsenic speciation in Scomberomorus niphonius by capillary electrophoresis-inductively coupled plasma mass spectrometry].

    PubMed

    Chen, Fa-rong; Zheng, Li; Wang, Zhi-Guang; Sun, Jie; Han, Li-Hui; Wang, Xiao-ru

    2014-06-01

    A method for the detection of arsenocholine (AsC), arsenobetaine (AsB), As(III), dimethylarsinic (DMA), monomethylarsonic (MMA) and As (V) by capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS) was established. The results showed that the six species of arsenic were separated within 20 min under the optimized conditions. Good linearities of 6 arsenic species were observed in the range from 2 to 50 μg x L(-1) with the linear correlation greater than 0.996, the detection limits were 0.10-1.08 μg x L(-1) and the RSDs (n = 5) of the peak areas were smaller than 7%. The method was successfully adopted to the determination of the species in Scomberomorus niphonius. The recoveries were between 93% and 98%, and we found the arsenobetaine (AsB) was the main species in the sample. The method was suitable for the analysis of other biological samples with the advantages of good stability, less sample consumption, short analysis time and convenience.

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

    PubMed Central

    Liu, Guangliang; Cai, Yong

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1995-06-01

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

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

    SciTech Connect

    Havrilla, George Joseph; McIntosh, Kathryn Gallagher; Judge, Elizabeth; Dirmyer, Matthew R.; Campbell, Keri; Gonzalez, Jhanis J.

    2016-10-20

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

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

    PubMed

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

    2015-02-06

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

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

    USGS Publications Warehouse

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

    2009-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  8. Precise determination of seawater calcium using isotope dilution inductively coupled plasma mass spectrometry.

    PubMed

    Liu, Hou-Chun; You, Chen-Feng; Cai, Wei-Jun; Chung, Chuan-Hsiung; Huang, Kuo-Fang; Chen, Bao-Shan; Li, Yen

    2014-02-21

    We describe a method for rapid, precise and accurate determination of calcium ion (Ca(2+)) concentration in seawater using isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS). A 10 μL aliquot of seawater was spiked with an appropriate (43)Ca enriched solution for (44)Ca/(43)Ca ID-ICP-MS analyses, using an Element XR (Thermo Fisher Scientific), operated at low resolution in E-scan acquisition mode. A standard-sample bracketing technique was applied to correct for potential mass discrimination and ratio drift at every 5 samples. A precision of better than 0.05% for within-run and 0.10% for duplicate measurements of the IAPSO seawater standard was achieved using 10 μL solutions with a measuring time less than 3 minutes. Depth profiles of seawater samples collected from the Arctic Ocean basin were processed and compared with results obtained by the classic ethylene glycol tetra-acetic acid (EGTA) titration. Our new ID-ICP-MS data agreed closely with the conventional EGTA data, with the latter consistently displaying 1.5% excess Ca(2+) values, possibly due to a contribution of interference from Mg(2+) and Sr(2+) in the EGTA titration. The newly obtained Sr/Ca profiles reveal sensitive water mass mixing in the upper oceanic column to reflect ice melting in the Arctic region. This novel technique provides a tool for seawater Ca(2+) determination with small sample size, high throughput, excellent internal precision and external reproducibility.

  9. Determination of stable cesium and strontium in rice samples by inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Srinuttrakul, W.; Yoshida, S.

    2017-06-01

    For long-term radiation dose assessment models, food ingestion is one of the major exposure pathways to human. In general, the stable isotopes can serve as analogues of radioisotopes. In this study, rice samples were collected from 30 paddy fields in Si Sa Ket, Yasothon and Roi Et in the northeast of Thailand in November 2014. The concentrations of stable cesium (Cs-133) and strontium (Sr-88) in polished rice were determined by inductively coupled plasma mass spectrometry (ICP-MS). The standard reference material of rice flour (NIST 1568a) with spiked Cs and Sr was used to validate the analytical method. The concentration of Cs in polished rice from Si Sa Ket, Yasothon and Roi Et was 0.158 ± 0.167 mg kg-1, 0.090 ± 0.117 mg kg-1 and 0.054 ± 0.031 mg kg-1, respectively. The concentration of Sr in polished rice from Si Sa Ket, Yasothon and Roi Et was 0.351 ± 0.108 mg kg-1, 0.364 ± 0.215 mg kg-1 and 0.287 ± 0.102 mg kg-1, respectively. Comparison of the results with Japanese data before the Fukushima Di-ichi nuclear power plant accident showed that the concentrations of both Cs and Sr for Thai rice were higher than those for Japanese rice.

  10. Solid sampling electrothermal vaporization for sample introduction in inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Moens, L.; Verrept, P.; Boonen, S.; Vanhaecke, F.; Dams, R.

    1995-06-01

    Solid sampling using electrothermal vaporization is an attractive sample introduction method for atomic absorption spectrometry (AAS), inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). For AAS, the method is well established. The techniques needed to apply SS-ETV in ICP-based methods are described, with the emphasis on the coupling of different types of ETV-devices to the inductively coupled plasma torch and on the requirements for the spectrometer and the data acquisition and handling system. Though standardization is not straightforward, it is shown that standard addition and external calibration with solid standards yield accurate results. The latter is demonstrated by the analysis of standard reference materials. Figures of merit for SS-ETV-ICP-AES and SS-ETV-ICP-MS are presented. The literature concerning ICP-AES and ICP-MS (methods and applications) is briefly reviewed and new results of SS-ETV-ICP-MS analysis of SRMs are presented.

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

    SciTech Connect

    Luong, Elise

    1999-05-10

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

  12. Bioimaging of metals by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

    PubMed

    Becker, J Sabine; Zoriy, Miroslav; Matusch, Andreas; Wu, Bei; Salber, Dagmar; Palm, Christoph; Becker, J Susanne

    2010-01-01

    The distribution analysis of (essential, beneficial, or toxic) metals (e.g., Cu, Fe, Zn, Pb, and others), metalloids, and non-metals in biological tissues is of key interest in life science. Over the past few years, the development and application of several imaging mass spectrometric techniques has been rapidly growing in biology and medicine. Especially, in brain research metalloproteins are in the focus of targeted therapy approaches of neurodegenerative diseases such as Alzheimer's and Parkinson's disease, or stroke, or tumor growth. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) using double-focusing sector field (LA-ICP-SFMS) or quadrupole-based mass spectrometers (LA-ICP-QMS) has been successfully applied as a powerful imaging (mapping) technique to produce quantitative images of detailed regionally specific element distributions in thin tissue sections of human or rodent brain. Imaging LA-ICP-QMS was also applied to investigate metal distributions in plant and animal sections to study, for example, the uptake and transport of nutrient and toxic elements or environmental contamination. The combination of imaging LA-ICP-MS of metals with proteomic studies using biomolecular mass spectrometry identifies metal-containing proteins and also phosphoproteins. Metal-containing proteins were imaged in a two-dimensional gel after electrophoretic separation of proteins (SDS or Blue Native PAGE). Recent progress in LA-ICP-MS imaging as a stand-alone technique and in combination with MALDI/ESI-MS for selected life science applications is summarized. Copyright 2009 Wiley Periodicals, Inc.

  13. Direct solution introduction using conventional nebulizers with a short torch for plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Westphal, Craig S.; Montaser, Akbar

    2006-06-01

    -high efficiency nebulizer-short torch system is 3.1% and 3.7% based on peak areas and heights, respectively, at a solution uptake rate of 85 μL/min. Good agreement is obtained between certified and measured concentrations for several elements across the mass range (e.g., Al, V, Mn, As, Cd, Pb, U). The proposed system is novel because it potentially offers a lower-cost and a more universal arrangement for improved direct solution introduction in plasma mass spectrometry using off-the-shelf commercial nebulizers.

  14. Element residues in food contact plastics and their migration into food simulants, measured by inductively-coupled plasma-mass spectrometry.

    PubMed

    Fordham, P J; Gramshaw, J W; Crews, H M; Castle, L

    1995-01-01

    Polymers intended for food contact use have been analysed for inorganic residues which can be attributed to a range of substances employed as polymerization aids (e.g. catalysts), or to additives incorporated into the polymer to fulfil a specific task (e.g. lubricants). The migration of these residues into food simulants was studied. Residues were determined by using the multi-element capability of Inductively-Coupled Plasma-Mass Spectrometry (ICP-MS). Semi-quantitative analysis was carried out on acid digests of polymer materials, obtained by microwave heating in sealed Teflon containers. Limits of detection in the polymer were generally less than 1 mg/kg. Migration experiments were carried out with three food simulants and under two sets of conditions. Analysis for element residues was performed directly or, in the case of olive oil, on an emulsion of the simulant. Migration of certain elements into aqueous simulants was observed: Zr from polystyrene (650 micrograms/kg), Sb from polyethylene terephthalate (4 micrograms/kg) and Mg from acrylonitrile/butadiene/styrene copolymer (50 micrograms/kg). In all cases, where limits of detection permit, the levels which migrated from polymer to stimulant were less than proposed limits on migration.

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

    SciTech Connect

    Lorge, Susan Elizabeth

    2007-01-01

    Determining the composition of thin layers is increasingly important for a variety of industrial materials such as adhesives, coatings and microelectronics. Secondary ion mass spectrometry (SIMS), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), glow discharge optical emission spectroscopy (GDOES), glow discharge mass spectrometry (GDMS), and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) are some of the techniques that are currently employed for the direct analysis of the sample surface. Although these techniques do not suffer from the contamination problems that often plague sample dissolution studies, they do require matrix matched standards for quantification. Often, these standards are not readily available. Despite the costs of clean hoods, Teflon pipette tips and bottles, and pure acids, partial sample dissolution is the primary method used in the semiconductor industry to quantify surface impurities. Specifically, vapor phase decomposition (VPD) coupled to ICP-MS or total reflection x-ray fluorescence (TXRF) provides elemental information from the top most surface layers at detection sensitivities in the 107-1010atoms/cm2 range. The ability to quantify with standard solutions is a main advantage of these techniques. Li and Houk applied a VPD-like technique to steel. The signal ratio of trace element to matrix element was used for quantification. Although controlled dissolution concentrations determined for some of the dissolved elements agreed with the certified values, concentrations determined for refractory elements (Ti, Nb and Ta) were too low. LA-ICP-MS and scanning electron microscopy (SEM) measurements indicated that carbide grains distributed throughout the matrix were high in these refractory elements. These elements dissolved at a slower rate than the matrix element, Fe. If the analyte element is not removed at a rate similar to the matrix element a true

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

    PubMed

    Erdemir, Umran Seven; Gucer, Seref

    2014-11-05

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

  17. Lead concentrations and isotope ratios in street dust determined by electrothermal atomic absorption spectrometry and inductively coupled plasma mass spectrometry.

    PubMed

    Nageotte, S M; Day, J P

    1998-01-01

    A major source of environmental lead, particularly in urban areas, has been from the combustion of leaded petrol. Street dust has previously been used to assess urban lead contamination, and the dust itself can also be a potential source of lead ingestion, particularly to children. The progressive reduction of lead in petrol, in recent years, would be expected to have been reflected in a reduction of lead in urban dust. We have tested this hypothesis by repeating an earlier survey of Manchester street dust and carrying out a comparable survey in Paris. Samples were collected from streets and parks, lead was extracted by digestion with concentrated nitric acid and determined by electrothermal atomic absorption spectrometry. Lead isotope ratios were measured by inductively coupled plasma mass spectrometry. Results for Manchester show that lead concentrations have fallen by about 40% (street dust averages, 941 micrograms g-1 (ppm) in 1975 down to 569 ppm in 1997). In Paris, the lead levels in street dust are much higher and significant differences were observed between types of street (not seen in Manchester). Additionally, lead levels in parks were much lower than in Manchester. Samples collected under the Eiffel Tower had very high concentrations and lead isotope ratios showed that this was unlikely to be fallout from motor vehicles but could be due to the paint used on the tower. Isotope ratios measurements also revealed that lead additives used in France and the UK come from different sources.

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

    PubMed

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

    2011-08-01

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

  19. Multielemental analyses of environmental and geological samples by inductively coupled plasma mass spectrometry

    SciTech Connect

    Wu, Xiaowen.

    1993-01-01

    The technique of inductively coupled plasma-mass spectrometry (ICP-MS) has been applied to determine trace elements in environmental (drinking water and tree rings) and geological (soil) samples. Most of this monograph is focused on analysis in these samples of rare-earth elements and lead, which have lower detection limits in ICP-MS than in other analytical techniques. A brief history of ICP-MS and discussions of fundamental principles of the instrument, interferences of the method, and common analytical protocols are provided. The application of the technique to four projects is described: (1) Quantitative analysis of rare-earth elements in individual tree rings of fire-scarred trees was performed. The result showed that the concentrations of La, Pr, and Nd are highest in the ring corresponding to the fire year. (2) Lead pollution in drinking water from New York City was investigated by measuring lead concentration and the isotope ratio of [sup 206]Pb/[sup 207]Pb in drinking water samples and in the suspected polluting sources. It was found that lead in drinking water mainly comes from lead pipe and plumbing materials containing high concentrations of lead. In addition, optimization of the operating parameters and enhancement of lead signal were also discussed in the chapter. (3) Lead concentration in soil and in annual-growth rings of trees from streets in Brookyln, New York were analyzed. The change of lead concentration in the rings from 1952 to 1991 correlates with the consumption of lead in gasoline in the United States during the same period. The study showed that tree rings can be used as an indirect historical indicator of environmental changes during the tree's lifetime. (4) Rare-earth-element ratios in archaeological tree samples were measured to determine the original locations of the samples. In Appendix I, application of proton induced X-ray emission (PIXE) to analysis of wood samples is briefly discussed.

  20. Delta34S measurements of sulfur by multicollector inductively coupled plasma mass spectrometry.

    PubMed

    Clough, Robert; Evans, Peter; Catterick, Tim; Evans, E Hywel

    2006-09-01

    An accurate and precise method for the determination of delta34S measurements by multicollector inductively coupled plasma mass spectrometry has been developed. Full uncertainty budgets, taking into consideration all the uncertainties of the measurement process, have been calculated. The technique was evaluated by comparing measured values with a range of isotopically enriched sulfur solutions prepared by gravimetric addition of a 34S spike. The gravimetric and measured results exhibited a correlation of R2 >0.999. Repeat measurements were also made after adding Na (up to 420 microg g(-1)) and Ca (up to 400 microg g(-1)) salts to the sulfur standard. No significant deviations in the delta34S values were observed. The Russell correction expression (Ingle, C.; Sharp, B.; Horstwood, M.; Parrish, R.; Lewis, D. J. J. Anal. At. Spectrom. 2003, 18, 219) was used to correct for mass bias on the 34S/32S isotope amount ratio from the mass bias observed for the 30Si/28Si isotope amount ratio. Consistent compensation for instrumental mass bias was achieved. Resolution of the measured delta34S values was better than 1 per thousand after consideration of all uncertainty components. The technique was evaluated for practical applications by measurement of delta34S for a range of mineral waters by pneumatic nebulization sample introduction and the analysis of genuine and counterfeit pharmaceuticals using both laser ablation sample introduction and liquid chromatography. For the former two cases polyatomic interferences were resolved by operating the MC-ICPMS in medium resolution, while for the chromatographic analyses polyatomic interferences were minimized by the use of a membrane desolvator, allowing the instrument to be operated at a resolution of 400.

  1. Detecting nanoparticulate silver using single-particle inductively coupled plasma-mass spectrometry.

    PubMed

    Mitrano, Denise M; Lesher, Emily K; Bednar, Anthony; Monserud, Jon; Higgins, Christopher P; Ranville, James F

    2012-01-01

    The environmental prevalence of engineered nanomaterials, particularly nanoparticulate silver (AgNP), is expected to increase substantially. The ubiquitous use of commercial products containing AgNP may result in their release to the environment, and the potential for ecological effects is unknown. Detecting engineered nanomaterials is one of the greatest challenges in quantifying their risks. Thus, it is imperative to develop techniques capable of measuring and characterizing exposures, while dealing with the innate difficulties of nanomaterial detection in environmental samples, such as low-engineered nanomaterial concentrations, aggregation, and complex matrices. Here the authors demonstrate the use of inductively coupled plasma-mass spectrometry, operated in a single-particle counting mode (SP-ICP-MS), to detect and quantify AgNP. In the present study, two AgNP products were measured by SP-ICP-MS, including one of precisely manufactured size and shape, as well as a commercial AgNP-containing health food product. Serial dilutions, filtration, and acidification were applied to confirm that the method detected particles. Differentiation of dissolved and particulate silver (Ag) is a feature of the technique. Analysis of two wastewater samples demonstrated the applicability of SP-ICP-MS at nanograms per liter Ag concentrations. In this pilot study, AgNP was found at 100 to 200 ng/L in the presence of 50 to 500 ng/L dissolved Ag. The method provides the analytical capability to monitor Ag and other metal and metal oxide nanoparticles in fate, transport, stability, and toxicity studies using a commonly available laboratory instrument. Rapid throughput and element specificity are additional benefits of SP-ICP-MS as a measurement tool for metal and metal oxide engineered nanoparticles.

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

    USGS Publications Warehouse

    Long, James M.; Schaffler, James J.

    2013-01-01

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

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

    SciTech Connect

    Maxwell, S.; Jones, V.

    2009-05-27

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

  4. Rapid determination of actinides in urine by inductively coupled plasma mass spectrometry and alpha spectrometry: a hybrid approach.

    PubMed

    Maxwell, Sherrod L; Jones, Vernon D

    2009-11-15

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

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

    USGS Publications Warehouse

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

    1982-01-01

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

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

    EPA Science Inventory

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

  7. Identification of organically associated trace elements in wood and coal by inductively coupled plasma mass spectrometry.

    PubMed

    Richaud, R; Lazaro, M J; Lachas, H; Miller, B B; Herod, A A; Dugwell, D R; Kandiyoti, R

    2000-01-01

    1-Methyl-2-pyrrolidinone (NMP) was used to extract samples of wood (forest residue) and coal; the extracts were analysed by inductively coupled plasma mass spectrometry (ICP-MS) using two different sample preparation methods, in order to identify trace elements associated with the organic part of the samples. A sample of fly ash was similarly extracted and analysed in order to assess the behaviour of the mineral matter contained within the wood and coal samples. 32% of the biomass was extracted at the higher temperature and 12% at room temperature while only 12% of the coal was extracted at the higher temperature and 3% at room temperature. Less than 2% of the ash dissolved at the higher temperature. Size exclusion chromatograms of the extracts indicated the presence of significant amounts of large molecular mass materials (>1000 mu) in the biomass and coal extracts but not in the ash extract. Trace element analyses were carried out using ICP-MS on the acid digests prepared by 'wet ashing' and microwave extraction. Sixteen elements (As, Ba, Be, Cd, Co, Cr, Cu, Ga, Mn, Mo, Ni, Pb, Sb, Se, V and Zn) were quantified, in the samples before extraction, in the extracts and in the residues. Concentrations of trace elements in the original biomass sample were lower than in the coal sample while the concentrations in the ash sample were the highest. The major trace elements in the NMP extracts were Ba, Cu, Mn and Zn from the forest residue; Ba, Cu, Mn, Pb and Zn from the coal; Cu and Zn from the ash. These elements are believed to be associated with the organic extracts from the forest residue and coal, and also from the ash. Be and Sb were not quantified in the extracts because they were present at too low concentrations; up to 40% of Mn was extracted from the biomass sample at 202 degrees C, while Se was totally extracted from the ash sample. For the forest residue, approximately 7% (at room temperature) and 45% (at 202 degrees C) of the total trace elements studied were

  8. Investigation of lanthanum-strontium-cobalt ferrites using laser ablation inductively coupled plasma-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Óvári, Mihály; Tarsoly, Gergely; Németh, Zoltán; Mihucz, Victor G.; Záray, Gyula

    2017-01-01

    In the present study, suitability of laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for characterization of the purity and homogeneity of lanthanum-strontium-cobalt ferrite (LSCF) ceramic microsamples with general formula La1 - xSrxFe0.025Co0.975O3 (0.00 ≤ x ≤ 0.50) was studied through determination of their Sr:La ratios as well as Sr content either in depth or line profiling mode. The Sr content of the LSCF samples expressed as weight percent ranged between 5.8% and 9.7% in the case of wet chemical ICP-MS analysis, while theoretical values varied from 5.5% to 9.4%. In the case of LA-ICP-MS, relative standard deviation of the La-normalized Sr intensities was sufficient to characterize the homogeneity of the studied samples. Major and trace element (Mn, Ni, Cu, Mg, Al, Ba) concentrations could be detected at medium resolution of the applied sector field ICP-MS instrument after microwave-assisted acid digestion. For depth and line profiling, a successful approach consisted of the normalization of intensities of Sr, Fe and Co with the corresponding La counts. For the determination of the elemental ratios of La and Sr, the methods involving LA were in good agreement with theoretical values by standardization to an in-house standard corresponding to the LSCF sample having the highest x value (i.e., 0.50) checked by wet chemical ICP-MS measurements. Thus, assessment of fine scale doping of synthesized perovskite type of microsamples could be achieved by the proposed LA-ICP-MS based on a novel calibration approach applying an in-house perovskite standard. Therefore, LA-ICP-MS can be recommended for quality control of perovskite-based products. In memoriam Attila Vértes (1934-2011), full professor of the Institute of Chemistry, Eötvös Loránd University, Budapest, Hungary.

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

    NASA Astrophysics Data System (ADS)

    Arnquist, Isaac J.; Holcombe, James A.

    2012-10-01

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

  10. {sup 99}Tc bioassay by inductively coupled plasma mass spectrometry (ICP-MS)

    SciTech Connect

    Lewis, L.A.

    1998-05-01

    A means of analyzing {sup 99}Tc in urine by inductively coupled plasma mass spectrometry (ICP-MS) has been developed. Historically, {sup 99}Tc analysis was based on the radiometric detection of the 293 keV E{sub Max} beta decay product by liquid scintillation or gas flow proportional counting. In a urine matrix, the analysis of{sup 99}Tc is plagued with many difficulties using conventional radiometric methods. Difficulties originate during chemical separation due to the volatile nature of Tc{sub 2}O{sub 7} or during radiation detection due to color or chemical quenching. A separation scheme for {sup 99}Tc detection by ICP-MS is given and is proven to be a sensitive and robust analytical alternative. A comparison of methods using radiometric and mass quantitation of {sup 99}Tc has been conducted in water, artificial urine, and real urine matrices at activity levels between 700 and 2,200 dpm/L. Liquid scintillation results based on an external standard quench correction and a quench curve correction method are compared to results obtained by ICP-MS. Each method produced accurate results, however the precision of the ICP-MS results is superior to that of liquid scintillation results. Limits of detection (LOD) for ICP-MS and liquid scintillation detection are 14.67 and 203.4 dpm/L, respectively, in a real urine matrix. In order to determine the basis for the increased precision of the ICP-MS results, the detection sensitivity for each method is derived and measured. The detection sensitivity for the {sup 99}Tc isotope by ICP-MS is 2.175 x 10{sup {minus}7} {+-} 8.990 x 10{sup {minus}9} and by liquid scintillation is 7.434 x 10{sup {minus}14} {+-} 7.461 x 10{sup {minus}15}. A difference by seven orders of magnitude between the two detection systems allows ICP-MS samples to be analyzed for a period of 15 s compared to 3,600 s by liquid scintillation counting with a lower LOD.

  11. Novel Imprinted Polymer for the Preconcentration of Cadmium with Determination by Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Yilmaz, Vedat; Yilmaz, Hayriye; Arslan, Zikri; Leszczynski, Jerzy

    2017-01-01

    A novel Cd(II)-imprinted polymer was prepared with chemical immobilization approach by using N-methacryloyl-L-histidine as a vinylated chelating agent for on-line solid phase extraction of Cd(II) for determination by inductively coupled plasma mass spectrometry. Cd(II)-monomer complex was synthesized and copolymerized via bulk polymerization method in the presence of ethyleneglycoldimethacrylate cross-linker. The resulting polymer was leached with 1.0 mol L(-1) HNO3 to generate the cavities in the polymer for Cd(II) ions. The experimental conditions, including load pH, solution flow rate, and eluent concentration for effective sorption of Cd(II) were optimized using a minicolumn of the imprinted polymer. A volume of 5.0 mL sample 5 μg L(-1) Cd(II) solution at pH 6.5 was loaded onto the column at 2.0 mL min(-1) by using a sequential injection system (FIALab 3200) followed by elution with 1.0 mL of 0.75 mol L(-1) HNO3. The relative selectivity coefficients of the imprinted polymer for Cd(II) were 38.5, 3.5, 3.0, 2.5 and 6.0 in the presence of Cu(II), Ni(II), Zn(II), Co(II) and Pb(II), respectively. Computational calculations revealed that the selectivity of the imprinted polymer was mediated by the stability of Cd(II)-N-methacryloyl-L-histidine complex which was far more stable than those of commonly used monomers, such as 4-vinyl pyridine, methacrylic acid and vinylimidazole. The detection limit (3s) and relative standard deviation (%) were found to be 0.004 μg L(-1) and 3.2%, respectively. The method was validated by analysis of seawater certified reference material (CASS-4) and successfully applied to the determination of Cd(II) in coastal seawater and estuarine water samples.

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

    PubMed

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

    2016-09-01

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

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

    SciTech Connect

    Perdian, David C.

    2009-01-01

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

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

    ERIC Educational Resources Information Center

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

    2016-01-01

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

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

    EPA Science Inventory

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

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

    ERIC Educational Resources Information Center

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

    2016-01-01

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

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

    EPA Science Inventory

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

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

    EPA Science Inventory

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

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

    EPA Science Inventory

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

  20. Elemental labelling combined with liquid chromatography inductively coupled plasma mass spectrometry for quantification of biomolecules: A review

    PubMed Central

    Kretschy, Daniela; Koellensperger, Gunda; Hann, Stephan

    2012-01-01

    This article reviews novel quantification concepts where elemental labelling is combined with flow injection inductively coupled plasma mass spectrometry (FI-ICP-MS) or liquid chromatography inductively coupled plasma mass spectrometry (LC–ICP-MS), and employed for quantification of biomolecules such as proteins, peptides and related molecules in challenging sample matrices. In the first sections an overview on general aspects of biomolecule quantification, as well as of labelling will be presented emphasizing the potential, which lies in such methodological approaches. In this context, ICP-MS as detector provides high sensitivity, selectivity and robustness in biological samples and offers the capability for multiplexing and isotope dilution mass spectrometry (IDMS). Fundamental methodology of elemental labelling will be highlighted and analytical, as well as biomedical applications will be presented. A special focus will lie on established applications underlining benefits and bottlenecks of such approaches for the implementation in real life analysis. Key research made in this field will be summarized and a perspective for future developments including sophisticated and innovative applications will given. PMID:23062431

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

    SciTech Connect

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

    2013-08-08

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

  2. A critical review of inductively coupled plasma-mass spectrometry for geoanalysis, geochemistry and hydrology, Part 1. Analytical performance

    USGS Publications Warehouse

    Brenner, I.B.; Taylor, H.E.

    1992-01-01

    Present-day inductively coupled plasma-mass spectrometry (ICP-MS) instrumentation is described briefly. Emphasis is placed on performance characteristics for geoanalysis, geochemistry, and hydrology. Applications where ICP-MS would be indispensable are indicated. Determination of geochemically diagnostic trace elements (such as the rare earth elements [REE], U and Th), of isotope ratios for fingerprinting, tracer and other geo-isotope applications, and benchmark isotope dilution determinations are considered to be typical priority applications for ICP-MS. It is concluded that ICP-MS furnishes unique geoanalytical and environmental data that are not readily provided by conventional spectroscopic (emission and absorption) techniques.

  3. Determination of 20 trace elements and arsenic species for a realgar-containing traditional Chinese medicine Niuhuang Jiedu tablets by direct inductively coupled plasma-mass spectrometry and high performance liquid chromatography-inductively coupled plasma-mass spectrometry.

    PubMed

    Jin, Pengfei; Liang, Xiaoli; Xia, Lufeng; Jahouh, Farid; Wang, Rong; Kuang, Yongmei; Hu, Xin

    2016-01-01

    Niuhuang Jiedu tablet (NHJDT) is a realgar-containing traditional Chinese medicine. A direct inductively coupled plasma-mass spectrometry (ICP-MS) method for the simultaneous determination of 20 trace elements (Mg, K, Ca, Na, Fe, As, Zn, Sr, Ba, Cu, Mn, Ni, Pb, V, Cr, Se, Co, Mo, Cd, Hg) in NHJDT, as well as in water, gastric fluid and intestinal fluid was established. Meanwhile, a high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) method was developed for the determination of arsenite (As(III)), arsenate (As(V)), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and for the identification of arsenobetaine (AsB) and arsenocholine (AsC) in these extracts. Both methods were fully validated in the respect of linearity, sensitivity, precision, stability and accuracy. The reliability of the ICP-MS method was further evaluated using a certified standard reference material prepared from dried tomato leaves (NIST, SRM 1572a). The analysis showed that some manufacturers formulated lower amount of realgar than required in the Chinese Pharmacopoeia (ChP) in their preparations. In addition, almost same extraction profiles for total As and inorganic As were found in water and in gastrointestinal fluids, while higher extraction rates for other 19 elements were observed in gastrointestinal fluids. Our findings show that the toxicities of Hg, Cu, Cd and Pb in NHJDP are low, while the real As toxicity in NHJDT should be deeply investigated.

  4. Comparison of Analytical Methods for the Determination of Uranium in Seawater Using Inductively Coupled Plasma Mass Spectrometry

    SciTech Connect

    Wood, Jordana R.; Gill, Gary A.; Kuo, Li-Jung; Strivens, Jonathan E.; Choe, Key-Young

    2016-04-20

    Trace element determinations in seawater by inductively coupled plasma mass spectrometry are analytically challenging due to the typically very low concentrations of the trace elements and the potential interference of the salt matrix. In this study, we did a comparison for uranium analysis using inductively coupled plasma mass spectrometry (ICP-MS) of Sequim Bay seawater samples and three seawater certified reference materials (SLEW-3, CASS-5 and NASS-6) using seven different analytical approaches. The methods evaluated include: direct analysis, Fe/Pd reductive precipitation, standard addition calibration, online automated dilution using an external calibration with and without matrix matching, and online automated pre-concentration. The method which produced the most accurate results was the method of standard addition calibration, recovering uranium from a Sequim Bay seawater sample at 101 ± 1.2%. The on-line preconcentration method and the automated dilution with matrix-matched calibration method also performed well. The two least effective methods were the direct analysis and the Fe/Pd reductive precipitation using sodium borohydride

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

    NASA Astrophysics Data System (ADS)

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

    2009-11-01

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

  6. Determination of Hg in seawater by inductively coupled plasma mass spectrometry after on-line pre-concentration

    NASA Astrophysics Data System (ADS)

    Seibert, Edson Luiz; Dressler, Valderi Luiz; Pozebon, Dirce; Curtius, Adilson José

    2001-10-01

    A method for the determination of Hg in seawater by inductively coupled plasma mass spectrometry, after an on-line separation and pre-concentration, is described. The matrix separation was accomplished by retention of the Hg complex with the ammonium salt of O, O-diethyl dithiophosphoric acid on C 18 immobilized on silica in a micro-column. Before pre-concentration, the seawater sample was acidified with HNO 3 to 0.14 mol l -1. Methanol was used as the eluent, which was introduced into the conventional pneumatic nebulizer of the instrument. External calibration with aqueous analytical solutions, submitted to the same procedure, was used. An enhancement factor of 16 was obtained, and the limit of detection was 5 ng l -1. The sample consumption was 2.3 ml per determination, and the sampling frequency was 21 h -1. The accuracy was tested by comparison with vapor generation inductively coupled plasma mass spectrometry. The agreement between the Hg concentrations measured by the two methods in the seawater samples was good.

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

    SciTech Connect

    Leach, James

    1999-02-12

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

  8. New approach to the determination phosphorothioate oligonucleotides by ultra high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry.

    PubMed

    Studzińska, Sylwia; Mounicou, Sandra; Szpunar, Joanna; Łobiński, Ryszard; Buszewski, Bogusław

    2015-01-15

    This text presents a novel method for the separation and detection of phosphorothioate oligonucleotides with the use of ion pair ultra high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry The research showed that hexafluoroisopropanol/triethylamine based mobile phases may be successfully used when liquid chromatography is coupled with such elemental detection. However, the concentration of both HFIP and TEA influences the final result. The lower concentration of HFIP, the lower the background in ICP-MS and the greater the sensitivity. The method applied for the analysis of serum samples was based on high resolution inductively coupled plasma mass spectrometry. Utilization of this method allows determination of fifty times lower quantity of phosphorothioate oligonucleotides than in the case of quadrupole mass analyzer. Monitoring of (31)P may be used to quantify these compounds at the level of 80 μg L(-1), while simultaneous determination of sulfur is very useful for qualitative analysis. Moreover, the results presented in this paper demonstrate the practical applicability of coupling LC with ICP-MS in determining phosphorothioate oligonucleotides and their metabolites in serum within 7 min with a very good sensitivity. The method was linear in the concentration range between 0.2 and 3 mg L(-1). The limit of detection was in the range of 0.07 and 0.13 mg L(-1). Accuracy varied with concentration, but was in the range of 3%. Copyright © 2014 Elsevier B.V. All rights reserved.

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

    PubMed

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

    2015-12-01

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

  10. Mechanism of vaporization of yttrium and rare earth elements in electrothermal vaporization inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Goltz, D. M.; Grégoire, D. C.; Chakrabarti, C. L.

    1995-09-01

    The mechanism of vaporization of yttrium and the rare earth elements (REEs) has been studied using graphite furnace atomic absorption spectrometry (GFAAS) and inductively-coupled plasma mass spectrometry (ICP-MS). The appearance temperatures for Y and the REEs obtained by GFAAS were generally identical to the appearance temperatures obtained using ETV-ICP-MS. At lower temperatures, Y and the REEs are predominantly vaporized in atomic form or as oxides, while at temperatures above 2500°C, the elements are vaporized as oxides and/or carbides. This accounts for the very high sensitivity of ETV-ICP-MS compared to GFAAS for the determination of these elements. Absolute limits of detection for Y and all of the REEs using ETV-ICP-MS ranged from 0.002 pg for Tm to 0.2 pg for Ce. The use of freon as a chemical modifier was effective in controlling analyte carbide formation and reducing memory effects.

  11. Screening hydrolysis products of sulfur mustard agents by high-performance liquid chromatography with inductively coupled plasma mass spectrometry detection.

    PubMed

    Kroening, Karolin K; Richardson, Douglas D; Afton, Scott; Caruso, Joseph A

    2009-04-01

    Sulfur mustard (HD), bis(2-chloroethyl)sulfide, is one of a class of mustard agents which are chemical warfare agents. The main chemical warfare hydrolysis degradation products of sulfur mustards are: thiodiglycol, bis(2-hydroxyethylthio)methane, 1,2-bis(2-hydroxyethylthio)ethane, 1,3-bis(2-hydroxyethylthio)propane, and 1,4-bis(2-hydroxyethylthio)butane. The aim of this study is to identify these five hydrolysis degradation products utilizing reversed-phase high-performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (ICP-MS) for element-specific sulfur detection using a collision/reaction cell and electrospray ionization mass spectrometry to confirm the identification. To date, this is the first study utilizing ICP-MS with (32)S element-specific detection for the analysis of vesicant chemical warfare agent degradation products.

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

    PubMed

    Peterson, Dominic S; Montoya, Velma M

    2009-08-01

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

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

    PubMed

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

    2003-10-01

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

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

    SciTech Connect

    Peterson, Dominic S

    2008-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2004-06-01

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

  16. Differentiation of bullet type based on the analysis of gunshot residue using inductively coupled plasma mass spectrometry.

    PubMed

    Udey, Ruth N; Hunter, Brian C; Smith, Ruth Waddell

    2011-09-01

    Porcine tissue samples shot with two different types of bullets, jacketed and nonjacketed, were collected in the fresh state and throughout moderate decomposition. Wound samples were microwave-digested and analyzed using inductively coupled plasma mass spectrometry (ICP-MS) to detect all elements present at measurable levels in gunshot residue (GSR). Elements detected included antimony (Sb), barium (Ba), and lead (Pb), which are considered characteristic of GSR, as well as iron (Fe) and copper (Cu). These five elements were used to differentiate shot tissue and unshot tissue, as well as tissue shot by the two different bullet types, both in the fresh state and throughout moderate decomposition. The concentrations of Cu, Sb, and Pb were able to distinguish the two bullet types in fresh tissue samples at the 95% confidence level. Cu and Pb were able to differentiate the bullet types throughout moderate decomposition at the 99% confidence level.

  17. Detection of gunshot residue in blowfly larvae and decomposing porcine tissue using inductively coupled plasma mass spectrometry (ICP-MS).

    PubMed

    Lagoo, Lisa; Schaeffer, Luther S; Szymanski, David W; Smith, Ruth Waddell

    2010-05-01

    Blowfly larvae and porcine tissue contaminated with gunshot residue (GSR) were collected during summer and winter months, over a 37-day and a 60-day sampling period, respectively. Wound samples were microwave-digested and analyzed by inductively coupled plasma mass spectrometry (ICP-MS) for the detection of antimony, barium, and lead. During summer, the 37-day sampling period encompassed all stages of decomposition, except skeletonization. The three elements were detected in larvae only on days 3 and 4 after death but were detected at significant levels in tissue samples throughout the entire sampling period. In winter, no significant decomposition was observed throughout the 60-day sampling. Although temperatures were too low for blowfly activity, the three elements were detected in the tissue samples at relatively constant, significant levels. Hence, GSR determination in tissue was more dependent on decomposition stage rather than time since death.

  18. Aluminium content of some processed foods, raw materials and food additives in China by inductively coupled plasma-mass spectrometry.

    PubMed

    Deng, Gui-Fang; Li, Ke; Ma, Jing; Liu, Fen; Dai, Jing-Jing; Li, Hua-Bin

    2011-01-01

    The level of aluminium in 178 processed food samples from Shenzhen city in China was evaluated using inductively coupled plasma-mass spectrometry. Some processed foods contained a concentration of up to 1226 mg/kg, which is about 12 times the Chinese food standard. To establish the main source in these foods, Al levels in the raw materials were determined. However, aluminium concentrations in raw materials were low (0.10-451.5 mg/kg). Therefore, aluminium levels in food additives used in these foods was determined and it was found that some food additives contained a high concentration of aluminium (0.005-57.4 g/kg). The results suggested that, in the interest of public health, food additives containing high concentrations of aluminium should be replaced by those containing less. This study has provided new information on aluminium levels in Chinese processed foods, raw materials and a selection of food additives.

  19. Comparison of serum zinc levels measured by inductively coupled plasma mass spectrometry in preschool children with febrile and afebrile seizures.

    PubMed

    Lee, Jun-Hwa; Kim, Jeong Hyun

    2012-05-01

    Changes in levels of trace elements have been proposed to underlie febrile seizures. Particularly, low zinc levels have been proposed as related factor of febrile seizure. In this study, we investigated whether mean serum zinc levels differed between children with febrile seizure and afebrile seizure. Using inductively coupled plasma mass spectrometry, serum zinc levels were measured in 288 children who had been diagnosed with febrile seizures (N=248) and afebrile seizures (N=40). Mean serum zinc levels were compared between the 2 groups. Mean serum zinc level was 60.5±12.7 µg/dL in the febrile seizure group and 68.9 ±14.5 µg/dL in the afebrile seizure group. A significant difference in serum zinc levels was observed between the febrile and afebrile seizure groups (P<0.001). Zinc levels in children with febrile seizure were significantly lower than those in children with afebrile seizure.

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

    SciTech Connect

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

    1988-12-01

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

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

    PubMed

    Krzciuk, Karina

    2016-07-03

    Inductively coupled plasma-mass spectrometry (ICP-MS) is a popular and routine analytical method that has been used for determination of trace elements since the 1980s. It provides fast quantitative analysis and allows the determination of more than 70 elements with good accuracy and very low detection limits, but requires an intricate calibration procedure. In analyses of samples for which very low detection limits are not required a semiquantitative ICP-MS analysis mode can be used. This approach is more time- and cost-effective, and it uses a simple calibration procedure. This article presents a critical review of the semiquantitative (SQ) mode of ICP-MS and describes current and future applications of SQ analysis.

  2. Using laser ablation/inductively coupled plasma mass spectrometry to bioimage multiple elements in mouse tumors after hyperthermia.

    PubMed

    Hsieh, Yi-Kong; Jiang, Pei-Shin; Yang, Bing-Shen; Sun, Tian-Ye; Peng, Hsu-Hsia; Wang, Chu-Fang

    2011-08-01

    In this study, we employed laser ablation/inductively coupled plasma mass spectrometry (LA-ICP-MS) to map the spatial distribution of Gd-doped iron oxide nanoparticles (IONPs) in one tumor slice that had been subjected to magnetic fluid hyperthermia (MFH). The mapping results revealed the high resolution of the elemental analysis, with the distribution of Gd atoms highly correlated with that of the Fe atoms. The spatial distributions of C, P, S, and Zn atoms revealed that the effect of MFH treatment was significantly dependent on the diffusion of the magnetic fluid in the tissue. An observed enrichment of Cu atoms after MFH treatment was probably due to inflammation in the tumor. The abnormal distribution of Ni atoms suggests a probable biochemical reaction in the tumor. Therefore, this LA-ICP-MS mapping technique can provide novel information regarding the spatial distribution of elements in tumors after cancer therapy.

  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. Investigating Uranium Concentrations in Groundwaters in the State of Idaho Using Kinetic Phosphorescence Analysis and Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Tkavadze, Levan; Dunker, Roy E; Brey, Richard R; Dudgeon, John

    2016-11-01

    The determination of uranium concentrations in natural water samples is of great interest due to the environmental consequences of this radionuclide. In this study, 380 groundwater samples from various locations within the state of Idaho were analyzed using two different techniques. The first method was Kinetic Phosphorescence Analysis (KPA), which gives the total uranium concentrations in water samples. The second analysis method was inductively coupled plasma mass spectrometry (ICP- MS). This method determines the total uranium concentration as well as the separate isotope concentrations of uranium. The U/U isotopic ratio was also measured for each sample to confirm that there was no depleted or enriched uranium present. The results were compared and mapped separately from each other. The study also found that in some areas of the state, natural uranium concentrations are relatively high.

  5. Separation and identification of oligonucleotides by hydrophilic interaction liquid chromatography (HILIC) - inductively coupled plasma mass spectrometry (ICPMS)

    PubMed Central

    Easter, Renee N.; Kröning, Karolin K.; Caruso, Joseph A.; Limbach, Patrick A.

    2012-01-01

    A method for the separation and detection of oligonucleotides utilizing hydrophilic interaction liquid chromatography (HILIC) with inductively coupled plasma mass spectrometry (ICPMS) is described. Polythymidilic acids of various lengths (10, 15, 20 and 30 nucleotides) were separated under gradient HILIC conditions. Selective detection of oligonucleotides was possible through monitoring m/z 47, corresponding to 31P16O+, using ICPMS. Oxygen was used as a reaction gas in the collision/reaction cell to produce PO+ by reacting with phosphorus in the gas phase, thereby effectively eliminating the interferences for phosphorus normally seen at m/z 31. Limits of detection (LODs) were determined to be 1.69 pmol, 1.21 pmol, 1.0 pmol and 0.55 pmol loaded on column for the 10, 15, 20 and 30-mer, respectively. PMID:20830328

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

    PubMed

    İzgi, Belgin; Kayar, Murat

    2015-07-01

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

  7. Comparison of ultraviolet femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry analysis in glass, monazite, and zircon.

    PubMed

    Poitrasson, Franck; Mao, Xianglei; Mao, Samuel S; Freydier, Rémi; Russo, Richard E

    2003-11-15

    We compared the analytical performance of ultraviolet femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). The benefit of ultrafast lasers was evaluated regarding thermal-induced chemical fractionation, that is otherwise well known to limit LA-ICPMS. Both lasers had a Gaussian beam energy profile and were tested using the same ablation system and ICPMS analyzer. Resulting crater morphologies and analytical signals showed more straightforward femtosecond laser ablation processes, with minimal thermal effects. Despite a less stable energy output, the ultrafast laser yielded elemental (Pb/U, Pb/Th) and Pb isotopic ratios that were more precise, repeatable, and accurate, even when compared to the best analytical conditions for the nanosecond laser. Measurements on NIST glasses, monazites, and zircon also showed that femtosecond LA-ICPMS calibration was less matrix-matched dependent and therefore more versatile.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

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

    PubMed

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

    2014-09-01

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

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

    PubMed

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

    2010-06-01

    Many procedures have been developed to measure the concentration of monomethylmercury (MeHg) from different sample matrices, and the use of stable isotopes of mercury now provides opportunities to determine its formation and degradation rates. Here, a modified procedure for measuring mercury isotopes in sediment samples that uses acid leaching-ion exchange-thiosulfate extraction (TSE) to isolate and purify the methylated mercury from the matrix is proposed. The latter is followed by aqueous-phase ethylation, purge and trap on Tenax, gas chromatography separation of ethylated mercury compounds, and inductively coupled plasma mass spectrometry detection. The new TSE procedure bridges together two well-known methods, the acid-leaching and distillation-derivatization procedures, offering the advantages of artifact-free formation of the first, and low detection limits and the possibility of quantification of individual isotopes of mercury of the second. The modified procedure retains the derivatization, purge and trap, and gas chromatography and inductively coupled plasma mass spectrometry (GC-ICP-MS) detection steps from the distillation-derivatization procedure, and eliminates the distillation step, which is not only laborious but also expensive, due to the high cost of installation and time-consuming cleaning process. Major advantages of the TSE procedure proposed include the extraction and analysis of a large number of samples in a short time, excellent analyte recoveries, and the lack of artifact formation. Sediment certified reference materials (CRMs), BCR 580 and IAEA 405, were used to test the TSE procedure accuracy. Recoveries between 94 to 106% and 95 to 96% were obtained for CRMs and spiked samples (Milli-Q(R) water), respectively. Comparisons among thiosulfate extraction, distillation, and acid-leaching procedures have shown good agreement of methylmercury values. Copyright 2010 SETAC.

  11. Determination of technetium-99 in aqueous samples by isotope dilution inductively coupled plasma-mass spectrometry

    SciTech Connect

    Beals, D.M.

    1992-09-01

    An isotope dilution/inductively coupled plasma mass spectrometric method (ID/ICP-MS) for measuring the concentration of technetium-99 in aqueous samples was developed at the Savannah River Technology Center (SRTC). The procedure is faster than radiometric techniques, is also less subject to interferences, and has equal or better detection limits. It is currently being used to measure the concentration of {sup 99}Tc in samples of Savannah River water collected in the vicinity of the Savannah River Site. In this method, one liter samples of water are spiked with {sup 97}Tc. After equilibration, the technetium is extracted from the sample with a chromatographic resin. Interfering elements, molybdenum and ruthenium, are either not retained by the resin or are washed off with dilute nitric acid. The technetium is then eluted with more concentrated nitric acid, and the {sup 99}Tc/{sup 97}Tc ratio in the eluant is measured with an ICP-MS. The {sup 99}Tc concentration in the original sample is calculated from the {sup 99}Tc/{sup 97}Tc ratio. The chemical recovery of the extraction procedure is greater than 90%. The detection limit of the instrument, taken as three times the background counts at m/z = 99, is 0.6 part per trillion (ppt). The detection limit of the procedure, taken as three times the standard deviation of several reagent blank analyses, is 0.33 pCi/L.

  12. Determination of technetium-99 in aqueous samples by isotope dilution inductively coupled plasma-mass spectrometry

    SciTech Connect

    Beals, D.M.

    1992-01-01

    An isotope dilution/inductively coupled plasma mass spectrometric method (ID/ICP-MS) for measuring the concentration of technetium-99 in aqueous samples was developed at the Savannah River Technology Center (SRTC). The procedure is faster than radiometric techniques, is also less subject to interferences, and has equal or better detection limits. It is currently being used to measure the concentration of {sup 99}Tc in samples of Savannah River water collected in the vicinity of the Savannah River Site. In this method, one liter samples of water are spiked with {sup 97}Tc. After equilibration, the technetium is extracted from the sample with a chromatographic resin. Interfering elements, molybdenum and ruthenium, are either not retained by the resin or are washed off with dilute nitric acid. The technetium is then eluted with more concentrated nitric acid, and the {sup 99}Tc/{sup 97}Tc ratio in the eluant is measured with an ICP-MS. The {sup 99}Tc concentration in the original sample is calculated from the {sup 99}Tc/{sup 97}Tc ratio. The chemical recovery of the extraction procedure is greater than 90%. The detection limit of the instrument, taken as three times the background counts at m/z = 99, is 0.6 part per trillion (ppt). The detection limit of the procedure, taken as three times the standard deviation of several reagent blank analyses, is 0.33 pCi/L.

  13. Matrix effects during phosphorus determination with quadrupole inductively coupled plasma mass spectrometry.

    PubMed

    Kovacevic, Miroslav; Goessler, Walter; Mikac, Nevenka; Veber, Marjan

    2005-09-01

    A quadrupole inductively coupled plasma mass spectrometer was evaluated for use in the detection of phosphorus. The influences of nitric acid and methanol (simulating the composition of a sample solution after nitric acid digestion) on phosphorus determination were studied using two different measuring methods at different plasma conditions: detection of phosphorus ions at m/z 31 and detection of phosphorus oxide ions at m/z 47. The existence of polyatomic interferences at m/z 31 and 47 was explored. Nitric acid and methanol are shown to be the sources of polyatomic ions and therefore cause poorer detection limits. Better detection limits were achieved in such matrices when phosphorus was detected as 31P+. The presence of methanol improves the system sensitivity towards phosphorus sevenfold; however, this positive effect is hindered by the high background signal due to carbon-based polyatomic ions. For samples with an organic matrix an appropriate mineralization procedure should be applied (high excess of nitric acid and high temperature) to quantitatively oxidize organic compounds to carbon dioxide, which is easily removed from the sample, in order to achieve correct results.

  14. Establishing human heart chromium, cobalt and vanadium concentrations by inductively coupled plasma mass spectrometry.

    PubMed

    Day, Patrick L; Eckdahl, Steven J; Maleszewski, Joseph J; Wright, Thomas C; Murray, David L

    2017-05-01

    Chromium, cobalt, and vanadium are used in metallic joint prosthesis. Case studies have associated elevated heart tissue cobalt concentrations with myocardial injury. To document the long term heart metal ion concentrations, a validated inductively coupled plasma mass spectroscopy (ICP-MS) method was needed. The method utilized a closed-vessel microwave digestion system to digest the samples. An ICP-MS method utilizing Universal Cell Technology was used to determine our target analyte concentrations. Accuracy was verified using reference materials. Precision, sensitivity, recovery and linearity studies were performed. This method was used to establish a reference range for a non-implant containing cohort of 80 autopsy human heart tissues RESULTS: This method demonstrated an analytic measurement range of 0.5-100ng/mL for each element. Accuracy was within ±10% of target value for each element. Within-run precision for each element was below 20% CV. The chromium, vanadium and cobalt concentrations (mean±SD) were 0.1523±0.2157μg/g, 0.0094±0.0211μg/g and 0.1039±0.1305μg/g respectively in 80 non-implant containing human heart tissue samples. This method provides acceptable recovery of the chromium, cobalt and vanadium in heart tissue; allowing assessment of the effects of metallic joint prosthesis on myocardial health. Copyright © 2017 Elsevier GmbH. All rights reserved.

  15. Atomic Absorption Spectroscopy, Atomic Emission Spectroscopy, and Inductively Coupled Plasma-Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Miller, Dennis D.; Rutzke, Michael A.

    Atomic spectroscopy has played a major role in the development of our current database for mineral nutrients and toxicants in foods. When atomic absorption spectrometers became widely available in the 1960s, the development of atomic absorption spectroscopy (AAS) methods for accurately measuring trace amounts of mineral elements in biological samples paved the way for unprecedented advances in fields as diverse as food analysis, nutrition, biochemistry, and toxicology (1). The application of plasmas as excitation sources for atomic emission spectroscopy (AES) led to the commercial availability of instruments for inductively coupled plasma - atomic emission spectroscopy (ICP-AES) beginning in the late 1970s. This instrument has further enhanced our ability to measure the mineral composition of foods and other materials rapidly, accurately, and precisely. More recently, plasmas have been joined with mass spectrometers (MS) to form inductively coupled plasma-mass spectrometer ICP-MS instruments that are capable of measuring mineral elements with extremely low detection limits. These three instrumental methods have largely replaced traditional wet chemistry methods for mineral analysis of foods, although traditional methods for calcium, chloride, iron, and phosphorus remain in use today (see Chap. 12).

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

    PubMed

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

    2010-12-03

    A new method for the determination of (237)Np and Pu isotopes in large soil samples has been developed that provides enhanced uranium removal to facilitate assay by inductively coupled plasma mass spectrometry (ICP-MS). This method allows rapid preconcentration and separation of plutonium and neptunium in large soil samples for the measurement of (237)Np and Pu isotopes by ICP-MS. (238)U can interfere with (239)Pu measurement by ICP-MS as (238)UH(+) mass overlap and (237)Np via (238)U peak tailing. The method provides enhanced removal of uranium by separating Pu and Np initially on TEVA Resin, then transferring Pu to DGA resin for additional purification. The decontamination factor for removal of uranium from plutonium for this method is greater than 1×10(6). Alpha spectrometry can also be applied so that the shorter-lived (238)Pu isotope can be measured successfully. (239) Pu, (242)Pu and (237)Np were measured by ICP-MS, while (236)Pu and (238)Pu were measured by alpha spectrometry. Copyright © 2010 Elsevier B.V. All rights reserved.

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

    SciTech Connect

    Maxwell, S.

    2010-07-26

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

  18. Rapid determination of (237)Np in soil samples by multi-collector inductively-coupled plasma mass spectrometry and gamma spectrometry.

    PubMed

    Yi, Xiaowei; Shi, Yanmei; Xu, Jiang; He, Xiaobing; Zhang, Haitao; Lin, Jianfeng

    A radiochemical procedure is developed for the determination of (237)Np in soil with multi-collector inductively-coupled plasma mass spectrometry (MC-ICP-MS) and gamma-spectrometry. (239)Np (milked from (243)Am) was used as an isotopic tracer for chemical yield determination. The neptunium in the soil is separated by thenoyl-trifluoracetone extraction from 1 M HNO3 solution after reducing Np to Np(IV) with ferrous sulfamate, and then purified with Dowex 1 × 2 anion exchange resin. (239)Np in the resulting solution is measured with gamma-spectrometry for chemical yield determination while the (237)Np is measured with MC-ICP-MS. Measurement results for soil samples are presented together with those for two reference samples. By comparing the determined value with the reference value of the (237)Np activity concentration, the feasibility of the procedure was validated.

  19. Characterization of cobalt pigments found in traditional Valencian ceramics by means of laser ablation-inductively coupled plasma mass spectrometry and portable X-ray fluorescence spectrometry.

    PubMed

    Pérez-Arantegui, J; Resano, M; García-Ruiz, E; Vanhaecke, F; Roldán, C; Ferrero, J; Coll, J

    2008-02-15

    In this work, a comparison of the performances of laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) and portable X-ray fluorescence (XRF) spectrometry for the characterization of cobalt blue pigments used in the decoration of Valencian ceramics is presented. Qualitative data on the elemental composition of the blue pigments obtained using both techniques show a good agreement. Moreover, the results clearly illustrate that potters utilized different kinds of cobalt pigments in different historical periods. While both techniques seem suitable for the proposed task, they show different strengths and weaknesses. Portable X-ray fluorescence spectrometry is a cheaper and totally non-destructive technique, capable of providing fast and reliable results at the mgg(-1) level. LA-ICPMS, on the other hand, offers a much higher detection power and better spatial resolution, but its use results in some sample damage (sample consumption at the mug level), while it is a more expensive and non-portable technique.

  20. Alleviation of interferences and reduction of sample memory in inductively coupled plasma mass spectrometry

    SciTech Connect

    Smith, F.G.

    1991-06-27

    A simple variation sample preparation and introduction allows the measurement of chlorine isotope ratios by inductively coupled plasma mass spectroscopy (ICP-MS). Dissolution of the sample in D{sub 2}O rather than H{sub 2}O attenuates the major polyatomic ion {sup 36}ArH{sup +} and frees m/z = 37 for determination of {sup 37}Cl{sup +}. The isotope ratio {sup 35}Cl/{sup 37}Cl in a 50 mg L{sup {minus}1} solution of Cl as LiCl is determined with a relative standard deviation (RDS) of 0.21%. A method for the determination of boron is a variety of biological samples is described. Sample material is fused with Na{sub 2}CO{sub 3} and boron is separated from matrix components by using Amberlite IRA-743 boron selective ion-exchange resin. Boron is eluted with 1% HNO{sub 3} and samples are introduced to an ICP-mass spectrometer with a direct injection nebulizer (DIN). Xenon is added at 10 or 37 mL min{sup {minus}1} to the aerosol gas flow of an argon ICP-mass spectrometer. Addition of Xe substantially reduces polyatomic ions such as N{sub 2}{sup +}, HN{sub 2}{sup +}, NO{sup +}, ArH{sup +}, ClO{sup +}, ArC{sup +}, ClOH{sup +}, ArN{sup +}, and ArO{sup +} and facilitates the measurement of Si, K, V, Cr, and Fe. Isotope ratios are determined with RSDs from 0.6% to 1.6%. 210 refs., 14 figs., 19 tabs.

  1. Enhancement of ion transmission and reduction of background and interferences in inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Hu, Ke

    1992-06-01

    An inductively coupled plasma-mass spectrometer (ICP-MS) (four stages of differential pumping) is described. The large sampling orifice (1.31 mm dia.) improves signals for metal ions and resists plugging. The ion lens deflects ions off center and then back on center into the differential pumping orifice; there is no photon stop in the center. Ion trajectories calculations SIMION show that only those ions that leave the skimmer on center are transmitted, whereas most other lenses used in ICP-MS transmit only ions that leave the skimmer off axis. Background with the Daly detector is 4 counts s(exp -1). This ICP-MS yields low levels of many troublesome polyatomic ions. Signals from refractory metal oxide ions are about 1 percent of the corresponding metal ion signals. Grounding the first electrode of the ion lens reduces matrix effects to approximately less than 20 percent loss in signal for Co(+), Y(+), or Cs(+) in presence of 10 mM Sr, Tm, or Pb. This latter lens setting causes only 30 percent loss in sensitivity compared to biassing the first lens. Matrix effects can also be mitigated by re-adjusting the voltage on the first lens with matrix present. Floating the metal cones at various potentials can improve the ion transmission by a factor of at least four to six. Also, floating the cones extends the upper end of linearity. Net result is more sensitivity and higher ion beam intensity than with a grounded skimmer and sampler. Furthermore, mass discrimination can be reduced.

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

    EPA Science Inventory

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

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

    EPA Science Inventory

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

  4. Determination of Total Arsenic and Speciation in Apple Juice by Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry: An Experiment for the Analytical Chemistry Laboratory

    ERIC Educational Resources Information Center

    He, Ping; Colon, Luis A.; Aga, Diana S.

    2016-01-01

    A two-part laboratory experiment was designed for upper-level analytical chemistry students to provide hands-on experience in the use of high performance liquid chromatography (HPLC) for separation and inductively coupled plasma mass spectrometry (ICP-MS) for detection. In the first part of the experiment, the students analyze total arsenic in…

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

    EPA Science Inventory

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

  6. Determination of Total Arsenic and Speciation in Apple Juice by Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry: An Experiment for the Analytical Chemistry Laboratory

    ERIC Educational Resources Information Center

    He, Ping; Colon, Luis A.; Aga, Diana S.

    2016-01-01

    A two-part laboratory experiment was designed for upper-level analytical chemistry students to provide hands-on experience in the use of high performance liquid chromatography (HPLC) for separation and inductively coupled plasma mass spectrometry (ICP-MS) for detection. In the first part of the experiment, the students analyze total arsenic in…

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

    EPA Science Inventory

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

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

    PubMed

    Hirata, Takafumi; Kon, Yoshiaki

    2008-03-01

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

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

    PubMed

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

    2004-07-01

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

  10. Provenance determination of oriental porcelain using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS).

    PubMed

    Bartle, Emma K; Watling, R John

    2007-03-01

    The sale of fraudulent oriental ceramics constitutes a large proportion of the illegal artifact and antique trade and threatens to undermine the legitimate international market. The sophistication and skill of forgers has reached a level where, using traditional appraisal by eye and hand, even the most experienced specialist is often unable to distinguish between a genuine and fraudulent piece. In addition, current provenancing techniques such as energy-dispersive X-ray fluorescence (EDXRF) spectrometry and thermoluminescence (TL) dating can result in significant damage to the artifact itself. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), a relatively nondestructive analytical technique, has been used for the provenance determination of materials based on geographical origin. The technique requires the production of a laser crater, c. 100 microm in diameter, which is essentially invisible to the naked eye. Debris from this crater is analyzed using ICP-MS, with the results forming the basis of the provenance establishment protocol. Chinese, Japanese, and English porcelain shards have been analyzed using this protocol and generic isotopic distribution patterns have been produced that enable the provenance establishment of porcelain artifacts to their country of production. Minor variations between elemental fingerprints of artifacts produced in the same country also indicate that it may be possible to further provenance oriental ceramics to a specific production region or kiln site.

  11. [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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

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

  13. Comparative analysis of ancient ceramics by neutron activation analysis, inductively coupled plasma-optical-emission spectrometry, inductively coupled plasma-mass spectrometry, and X-ray fluorescence.

    PubMed

    Tsolakidou, Alexandra; Kilikoglou, Vassilis

    2002-10-01

    The accurate measurement of the maximum possible number of elements in ancient ceramic samples is the main requirement in provenance studies. For this reason neutron activation analysis (NAA) and X-ray fluorescence (XRF) have been successfully used for most of the studies. In this work the analytical performance of inductively coupled plasma-optical-emission spectrometry (ICP-OES) and inductively coupled plasma-mass spectrometry (ICP-MS) has been compared with that of XRF and NAA for the chemical characterization of archaeological pottery. Correlation coefficients between ICP techniques and XRF or NAA data were generally better than 0.90. The reproducibility of data calculated on a sample prepared and analysed independently ten times was approximately 5% for most of the elements. Results from the ICP techniques were finally evaluated for their capacity to identify the same compositional pottery groups as results from XRF and NAA analysis, by use of multivariate statistics.

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

    SciTech Connect

    McIntyre, Sally M.

    2010-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Makonnen, Yoseif; Beauchemin, Diane

    2015-01-01

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

  16. Determination of multiple human arsenic metabolites employing high performance liquid chromatography inductively coupled plasma mass spectrometry

    PubMed Central

    Stice, Szabina; Liu, Guangliang; Matulis, Shannon; Boise, Lawrence H.; Cai, Yong

    2016-01-01

    During the metabolism of different arsenic-containing compounds in human, a variety of metabolites are produced with significantly varying toxicities. Currently available analytical methods can only detect a limited number of human metabolites in biological samples during one run due to their diverse characteristics. In addition, co-elution of species is often unnoticeable with most detection techniques leading to inaccurate metabolic profiles and assessment of toxicity. A high performance liquid chromatography inductively coupled mass spectrometry (HPLC-ICP-MS) method was developed that can identify thirteen common arsenic metabolites possibly present in human with special attention dedicated to thiolated or thiol conjugated arsenicals. The thirteen species included in this study are arsenite (AsIII), arsino-glutathione (As(GS)3), arsenate (AsV), monomethylarsonous acid (MMAIII), monomethylarsino-glutathione (MMAIII(GS)2), monomethylarsonic acid (MMAV), dimethylarsinous acid (DMAIII (from DMAIIII)), S-(dimethylarsinic)cysteine (DMAIII(Cys)), dimethylarsino-glutathione (DMAIII(GS)), dimethylarsinic acid (DMAV), dimethylmonothioarsinic acid (DMMTAV), dimethyldithioarsinic acid (DMDTAV), dimethylarsinothioyl glutathione (DMMTAV(GS)). The developed method was applied for the analysis of cancer cells that were incubated with Darinaparsin (DMAIII(GS)), a novel chemotherapeutic agent for refractory malignancies, and the arsenic metabolic profile obtained was compared to results using a previously developed method. This method provides a useful analytical tool which is much needed in unequivocally identifying the arsenicals formed during the metabolism of environmental arsenic exposure or therapeutic arsenic administration. PMID:26708625

  17. Microfluidic high performance liquid chromatography-chip hyphenation to inductively coupled plasma-mass spectrometry.

    PubMed

    Bishop, David P; Blanes, Lucas; Wilson, Alexander B; Wilbanks, Thor; Killeen, Kevin; Grimm, Rudolf; Wenzel, Ross; Major, Derek; Macka, Mirek; Clarke, David; Schmid, Robin; Cole, Nerida; Doble, Philip A

    2017-05-12

    The Agilent Chip Cube Interface is a microfluidic chip-based technology originally designed for nanospray molecular mass spectrometry in which the sample enrichment, nano-column, tubing, connectors and spray tip were integrated into a single biocompatible chip. Here we describe the hyphenation of the Chip Cube Interface to ICP-MS via modification of the standard HPLC chip design and a new total consumption nebuliser suitable for flow rates as low as 300nLmin(-1). The potential of the instrument to eliminate common nanoLC - ICP-MS shortcomings such as leaks, blockages and band-broadening was demonstrated via analysis of cyanocobalamin in equine plasma. The method was linear over three orders of magnitude with an r(2) of 0.9999, the peak area repeatability was 1.9% (n=7), and the detection limit was 14ngmL(-1). This novel configuration of the Chip Cube Interface coupled to ICP-MS is a suitable platform for the analysis of biomolecules associated with trace metals and speciation applications. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Chromatographic behavior of selenoproteins in rat serum detected by inductively coupled plasma mass spectrometry.

    PubMed

    Anan, Yasumi; Hatakeyama, Yoshiko; Tokumoto, Maki; Ogra, Yasumitsu

    2013-01-01

    Two major selenoproteins are present in mammalian serum: extracellular glutathione peroxidase (eGPx) and selenoprotein P (Sel P). The chromatographic behaviors of the two serum selenoproteins were compared in four rodent species, and the selenoproteins in rat serum were identified by measuring enzyme activity and Western blotting. The selenoproteins in rat serum showed a specific chromatographic behavior. In particular, rat eGPx was eluted faster than eGPxs of the other rodent species, although the amino-acid sequences of the rodent species were identical. The elution profiles of Se in rat serum obtained by inductively coupled plasma tandem mass spectrometry (ICP-MS-MS) and ICP-MS were compared. The tandem quadrupoles and the O₂ reaction/collision gas completely removed severe interferences with the Se speciation originating from the plasma source and the biological sample matrix. ICP-MS-MS under the O₂ mass shift mode gave us more accurate abundance ratios of Se than ICP-MS.

  19. A direct injection high-efficiency nebulizer for inductively coupled plasma mass spectrometry.

    PubMed

    McLean, J A; Zhang, H; Montaser, A

    1998-03-01

    A simple, relatively low-cost direct injection high-efficiency nebulizer (DIHEN) is introduced for argon inductively coupled plasma (Ar ICP) spectrometry. The DIHEN may be operated at solution uptake rates of 1-100 microL/min. Analytical performance indexes for the DIHEN and fundamental characteristics of the aerosol produced are obtained using an ICP mass spectrometer (ICPMS) and a two-dimensional phase Doppler particle analyzer (2D PDPA), respectively. Results are compared to those obtained with a conventional crossflow pneumatic nebulizer (PN), equipped with a Scott-type spray chamber. Droplet sizes and velocities produced with the DIHEN are smaller than those reported for the direct injection nebulizer (DIN). The DIHEN offers optimal sensitivity at low injector gas flow rates (approximately 0.25 L/min) and high rf power (approximately 1.5 kW). For the 17 elements tested, detection limits (ppt) and sensitivities achieved with the DIHEN (at 85 microL/min) are similar to, or better than, those obtained on the same instrument using the PN (at 1 mL/min). However, because the primary aerosol is injected directly into the plasma, oxide-to-metal ion ratios (MO+/M+) are high, as in the case of the DIN. The utility of the DIHEN for the analysis of small-volume samples is demonstrated by microscale flow injection analysis (muFIA) of Cr bound to human lung DNA. Detection of Cr at the femtogram level is feasible.

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

    PubMed

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

    2014-09-16

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

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

    PubMed

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

    2007-10-02

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

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

    PubMed

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

    2010-01-01

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

  3. Analysis of potassium iodate reduction in tissue homogenates using high performance liquid chromatography-inductively coupled plasma-mass spectrometry.

    PubMed

    Cao, Xiaoxiao; Ma, Wei; Liu, Liejun; Xu, Jing; Wang, Haiyan; Li, Xiuwei; Wang, Jiangqing; Zhang, Jianhua; Wang, Zexi; Gu, Yunyou

    2015-10-01

    Potassium iodate (KIO3) and potassium iodide (KI) are the major salt iodization agents used worldwide. Unlike iodide (I(-)), iodate (IO3(-)) should be reduced to I(-) before it can be effectively used by the thyroid. In this study, we developed a new method for analyzing IO3(-) and I(-) in tissue homogenates using high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). We further applied the method to demonstrate the KIO3 reduction process by tissues in vitro. The effects of KIO3 on the total antioxidative activity (TAA) and reduced nicotinamide adenine dinucleotide phosphate (NADPH) were also investigated here. Finally, we found that IO3(-) can be reduced to I(-) by tissue homogenates and IO3(-) irreversibly decreases the antioxidant capability of tissues. Our studies suggest that KIO3 might have a big effect on the redox balance of tissue and would further result in oxidative stress of organisms. Copyright © 2015 Elsevier GmbH. All rights reserved.

  4. Determination of platinum surface contamination in veterinary and human oncology centres using inductively coupled plasma mass spectrometry.

    PubMed

    Janssens, T; Brouwers, E E M; de Vos, J P; de Vries, N; Schellens, J H M; Beijnen, J H

    2015-09-01

    The objective of this study was to determine the surface contamination with platinum-containing antineoplastic drugs in veterinary and human oncology centres. Inductively coupled plasma mass spectrometry was used to measure platinum levels in surface samples. In veterinary and human oncology centres, 46.3 and 68.9% of the sampled surfaces demonstrated platinum contamination, respectively. Highest platinum levels were found in the preparation rooms (44.6 pg cm(-2)) in veterinary centres, while maximal levels in human centres were found in oncology patient-only toilets (725 pg cm(-2)). Transference of platinum by workers outside areas where antineoplastic drugs were handled was observed in veterinary and human oncology centres. In conclusion, only low levels of platinum contamination attributable to carboplatin were found in the sampled veterinary oncology centres. However, dispersion of platinum outside areas where antineoplastic drugs were handled was detected in veterinary and human oncology centres. Consequently, not only personnel, but also others may be exposed to platinum.

  5. Comparison of selenium determination in liver samples by atomic absorption spectroscopy and inductively coupled plasma-mass spectrometry.

    PubMed

    Miksa, Irina Rudik; Buckley, Carol L; Carpenter, Nancy P; Poppenga, Robert H

    2005-07-01

    Selenium (Se) is an essential trace element that is often deficient in the natural diets of domestic animal species. The measurement of Se in whole blood or liver is the most accurate way to assess Se status for diagnostic purposes. This study was conducted to compare hydride generation atomic absorption spectroscopy (HG-AAS) with inductively coupled plasma-mass spectrometry (ICP-MS) for the detection and quantification of Se in liver samples. Sample digestion was accomplished with magnesium nitrate and nitric acid for HG-AAS and ICP-MS, respectively. The ICP-MS detection was optimized for 82Se with yttrium used as the internal standard and resulted in a method detection limit of 0.12 microg/g. Selenium was quantified by both methods in 310 samples from a variety of species that were submitted to the Toxicology Laboratory at New Bolton Center (Kennett Square, PA) for routine diagnostic testing. Paired measurements for each sample were evaluated by a mean difference plot method. Limits of agreement were used to describe the maximum differences likely to occur between the 2 methods. Results suggest that under the specified conditions ICP-MS can be reliably used in place of AAS for quantitation of tissue Se at or below 2 microg/g to differentiate between adequate and deficient liver Se concentrations.

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

    PubMed

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

    2006-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

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

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

    USGS Publications Warehouse

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

    2011-01-01

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

  9. Comparison of Serum Zinc Levels Measured by Inductively Coupled Plasma Mass Spectrometry in Preschool Children with Febrile and Afebrile Seizures

    PubMed Central

    Lee, Jun-Hwa

    2012-01-01

    Background Changes in levels of trace elements have been proposed to underlie febrile seizures. Particularly, low zinc levels have been proposed as related factor of febrile seizure. In this study, we investigated whether mean serum zinc levels differed between children with febrile seizure and afebrile seizure. Methods Using inductively coupled plasma mass spectrometry, serum zinc levels were measured in 288 children who had been diagnosed with febrile seizures (N=248) and afebrile seizures (N=40). Mean serum zinc levels were compared between the 2 groups. Results Mean serum zinc level was 60.5±12.7 µg/dL in the febrile seizure group and 68.9 ±14.5 µg/dL in the afebrile seizure group. A significant difference in serum zinc levels was observed between the febrile and afebrile seizure groups (P<0.001). Conclusions Zinc levels in children with febrile seizure were significantly lower than those in children with afebrile seizure. PMID:22563553

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

    USGS Publications Warehouse

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

    2009-01-01

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

  11. Direct determination of mercury in cosmetic samples by isotope dilution inductively coupled plasma mass spectrometry after dissolution with formic acid.

    PubMed

    Gao, Ying; Shi, Zeming; Zong, Qinxia; Wu, Peng; Su, Jing; Liu, Rui

    2014-02-17

    A new method was proposed for the accurate determination of mercury in cosmetic samples based on isotopic dilution (ID)-photochemical vapor generation (PVG)-inductively coupled plasma mass spectrometry (ICP MS) measurement. Cosmetic samples were directly dissolved in formic acid solution and subsequently subjected to PVG for the reduction of mercury into vapor species following by ICP MS detection. Therefore, the risks of analyte contamination and loss were avoided. Highly enriched (201)Hg isotopic spike is added to cosmetics and the isotope ratios of (201)Hg/(202)Hg were measured for the quantitation of mercury. With ID calibration, the influences originating from sample matrixes for the determination of mercury in cosmetic samples have been efficiently eliminated. The effects of several experimental parameters, such as the concentration of the formic acid, and the flow rates of carrier gas and sample were investigated. The method provided good reproducibility and the detection limits were found to be 0.6 pg mL(-1). Finally, the developed method was successfully applied for the determination of mercury in six cosmetic samples and a spike test was performed to verify the accuracy of the method. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Simultaneous speciation of selenium and arsenic using elevated temperature liquid chromatography separation with inductively coupled plasma mass spectrometry detection

    NASA Astrophysics Data System (ADS)

    Le, X. C.; Li, X.-F.; Lai, V.; Ma, M.; Yalcin, S.; Feldmann, J.

    1998-08-01

    A method was developed for the simultaneous speciation of both arsenic and selenium based on the separation of arsenic and selenium species using high performance liquid chromatography (HPLC) under elevated column temperatures followed by dual-element detection using inductively coupled plasma mass spectrometry (ICPMS). Thirteen arsenic and selenium species, including arsenate, arsenite, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, arsenocholine, tetramethylarsonium, two arsenosugars, selenate, selenite, selenocystine and selenomethionine, were studied using this approach. The HPLC separation using 70°C constant column temperature resulted in an improved resolution and faster separation of arsenic and selenium species. Nearly baseline resolution of these species was achieved on a reversed phase C18 column using hexanesulfonate as an ion pair reagent. The ICPMS detection of m/ z 75, 77 and 78 enabled simultaneous monitoring of arsenic, selenium, and potential interfering species, such as ArCl. An application of the HPLC/ICPMS technique was demonstrated by the speciation of arsenic and selenium in canned tuna fish. Arsenobetaine and selenocystine were detected as the major arsenic and selenium species, respectively. The technique was also applied to a study on the metabolism of arsenosugars. Speciation of six arsenosugar metabolites in human urine was complete in 19 min at 70°C column temperature, compared to 37 min at room temperature.

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

    PubMed

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

    2012-03-06

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

  14. Elemental bio-imaging of trace elements in teeth using laser ablation-inductively coupled plasma-mass spectrometry.

    PubMed

    Hare, Dominic; Austin, Christine; Doble, Philip; Arora, Manish

    2011-05-01

    In this study we present the application of a novel laboratory method that employs laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to construct two-dimensional maps of trace elements in teeth. Teeth were sectioned longitudinally, embedded in resin and polished to a smooth surface. Data were generated by laser ablating the entire sectioned tooth surface. Elemental images were constructed using custom-built software. Quantified images of (66)Zn, (88)Sr, (111)Cd and (208)Pb, with a spatial resolution of 30 μm(2), were generated from three teeth. Concentrations were determined by single-point calibration against NIST SRM 1486 (bone meal). Zn and Sr concentrations were determined in the μg g(-1) range and Cd and Pb in the ng g(-1) range. Concentrations of Pb, Zn and Cd were higher in dentine particularly in regions adjacent the pulp. Elemental bio-imaging employing LA-ICP-MS is a novel method for constructing μm-scale maps of trace elements in teeth. This simple imaging method displays the heterogeneity of trace elements throughout the tooth structure that correspond to specific structural and developmental features of teeth. As a preliminary study, this work demonstrates the capabilities of LA-ICP-MS imaging in dental research. Copyright © 2011 Elsevier Ltd. All rights reserved.

  15. Determination of cadmium, mercury and lead in coal fly ash by slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Liao, Hsien-Chung; Jiang, Shiuh-Jen

    1999-08-01

    Ultrasonic slurry sampling electrothermal vaporization isotope dilution inductively coupled plasma mass spectrometry (USS-ETV-ID-ICP-MS) has been applied to the determination of Cd, Hg and Pb in coal fly ash samples. Thioacetamide (TAC) was used as the modifier. Since the sensitivities of the elements studied in coal fly ash slurry and aqueous solution were quite different, isotope dilution method was used for the determination of Cd, Hg and Pb in these coal fly ash samples. The isotope ratios of each element were calculated from the peak areas of each injection peak. This method has been applied to the determination of Cd, Hg and Pb in NIST SRM 1633a coal fly ash reference material and a coal fly ash sample collected from Kaohsiung area. Analysis results of reference sample NIST SRM 1633a coal fly ash agreed satisfactorily with the certified values. The other sample determined by isotope dilution and method of standard additions was agreed satisfactorily. Precision was better than 6% for most of the determinations and accuracy was better than 4% with the USS-ETV-ID-ICP-MS method. Detection limits estimated from standard addition curves were in the range of 24-58, 6-28 and 108-110 ng g-1 for Cd, Hg and Pb, respectively.

  16. Flow microcapillary plasma mass spectrometry-based investigation of new Al-Cr-Fe complex metallic alloy passivation.

    PubMed

    Ott, N; Beni, A; Ulrich, A; Ludwig, C; Schmutz, P

    2014-03-01

    Al-Cr-Fe complex metallic alloys are new intermetallic phases with low surface energy, low friction, and high corrosion resistance down to very low pH values (0-2). Flow microcapillary plasma mass spectrometry under potentiostatic control was used to characterize the dynamic aspect of passivation of an Al-Cr-Fe gamma phase in acidic electrolytes, allowing a better insight on the parameters inducing chemical stability at the oxyhydroxide-solution interface. In sulfuric acid pH 0, low element dissolution rates (in the µg cm(-2) range after 60 min) evidenced the passive state of the Al-Cr-Fe gamma phase with a preferential over-stoichiometric dissolution of Al and Fe cations. Longer air-aging was found to be beneficial for stabilizing the passive film. In chloride-containing electrolytes, ten times higher Al dissolution rates were detected at open-circuit potential (OCP), indicating that the spontaneously formed passive film becomes unstable. However, electrochemical polarization at low passive potentials induces electrical field generated oxide film modification, increasing chemical stability at the oxyhydroxide-solution interface. In the high potential passive region, localized attack is initiated with subsequent active metal dissolution.

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

    NASA Astrophysics Data System (ADS)

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

    2003-11-01

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

  18. Analysis of four toxic metals in a single rice seed by matrix solid phase dispersion -inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    He, Xiufen; Chen, Lixia; Chen, Xin; Yu, Huamei; Peng, Lixu; Han, Bingjun

    2016-12-01

    Toxic metals in rice pose great risks to human health. Metal bioaccumulation in rice grains is a criterion of breeding. Rice breeding requires a sensitive method to determine metal content in single rice grains to assist the variety selection. In the present study, four toxic metals of arsenic (As), cadmium (Cd), chromium (Cr) and lead (Pb) in a single rice grain were determined by a simple and rapid method. The developed method is based on matrix solid phase dispersion using multi-wall carbon nanotubes (MWCNTs) as dispersing agent and analyzed by inductively coupled plasma mass spectrometry. The experimental parameters were systematically investigated. The limits of detection (LOD) were 5.0, 0.6, 10 and 2.1 ng g-1 for As, Cd, Cr, and Pb, respectively, with relative standard deviations (n = 6) of <7.7%, demonstrating the good sensitivity and precision of the method. The results of 30 real world rice samples analyzed by this method agreed well with those obtained by the standard microwave digestion. The amount of sample required was reduced approximately 100 fold in comparison with the microwave digestion. The method has a high application potential for other sample matrices and elements with high sensitivity and sample throughput.

  19. Coupling centrifuge modeling and laser ablation inductively coupled plasma mass spectrometry to determine contaminant retardation in clays.

    PubMed

    Timms, Wendy; Hendry, M Jim; Muise, Jason; Kerrich, Robert

    2009-02-15

    Quantifying the retardation (Rd) of reactive solutes as they migrate through low-permeability clay-rich media is difficult, thus motivating this study to assess the viability of combining centrifuge modeling and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) techniques. An influent solution containing Cl-, trace metals, and lanthanide species flowed at 1.0 mL x h(-1) through an undisturbed clay-rich core sample (33 mm diameter x 50 mm long) mounted in a UFA Beckman centrifuge operating at 3000 rpm (N factor = 876 g). During the 87 day experiment the hydraulic conductivity of the core was 3.4 x 10(-10) m x s(-1). Effluent breakthrough data indicate the Rd of Tl to be 10; incomplete breakthrough (non-steady-state) data for 145Nd and 171Yb suggest Rd values of >75 and >85, respectively. At the completion of the transport experiment, longitudinal sections of the core solid were analyzed for 145Nd and 171Yb using a Cetac laser ablation system coupled with an ICP-MS. The longitudinal core sections yielded Rd values of >10000 for 145Nd and 171Yb. This study demonstrates coupling these techniques can provide Rd values for a wide range of reactive solutes with relatively rapid testing of small-scale, low hydraulic conductivity core samples.

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

    PubMed Central

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

    2017-01-01

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

  1. High levels of heavy metal accumulation in dental calculus of smokers: a pilot inductively coupled plasma mass spectrometry study.

    PubMed

    Yaprak, E; Yolcubal, I; Sinanoğlu, A; Doğrul-Demiray, A; Guzeldemir-Akcakanat, E; Marakoğlu, I

    2017-02-01

    Various trace elements, including toxic heavy metals, may exist in dental calculus. However, the effect of environmental factors on heavy metal composition of dental calculus is unknown. Smoking is a major environmental source for chronic toxic heavy metal exposition. The aim of this study is to compare toxic heavy metal accumulation levels in supragingival dental calculus of smokers and non-smokers. A total of 29 supragingival dental calculus samples were obtained from non-smoker (n = 14) and smoker (n = 15) individuals. Subjects with a probability of occupational exposure were excluded from the study. Samples were analyzed by inductively coupled plasma mass spectrometry in terms of 26 metals and metalloids, including toxic heavy metals. Toxic heavy metals, arsenic (p < 0.05), cadmium (p < 0.05), lead (p < 0.01), manganese (p < 0.01) and vanadium (p < 0.01) levels were significantly higher in smokers than non-smokers. The levels of other examined elements were similar in both groups (p > 0.05). Within the limitations of this study, it can be concluded that the elementary composition of dental calculus may be affected by environmental factors such as tobacco smoke. Therefore, dental calculus may be utilized as a non-invasive diagnostic biological material for monitoring chronic oral heavy metal exposition. However, further studies are required to evaluate its diagnostic potential. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  2. The quick and ultrasensitive determination of K in NaI using inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Arnquist, Isaac J.; Hoppe, Eric W.

    2017-04-01

    A highly sensitive, novel and quick assay method utilizing inductively coupled plasma mass spectrometry was developed for the determination of K in NaI powders and NaI(Tl) scintillator crystals for use in ultralow background applications. The determination of K (viz.40K), as well as Th and U and their daughters, is important in ultralow background detector materials to ensure incorporation of materials of sufficiently high radiopurity. Through the use of improved instrumentation, cool plasma operating conditions, and meticulously clean sample preparations, detection limits of 11 fg natK g-1 (or 341 pBq 40K kg-1) was attained for K in pure water. Detection limits in the sample matrix (i.e., NaI) were 0.529 ng natK g NaI-1 (or 16.4 μBq 40K kg NaI-1). A number of different precursor NaI powder samples and NaI(Tl) scintillator crystals were assayed for their K content. Determinations ranged from 0.757 to 31.4 ng natK g NaI-1. This method allows for the screening of materials to unprecedented levels in a fraction of the time compared to gamma ray counting techniques, providing a useful method for a more effective screening tool of K in ultralow background detector materials.

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

    PubMed

    Giussani, Barbara; Monticelli, Damiano; Rampazzi, Laura

    2009-03-02

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

  4. High-resolution laser ablation-inductively coupled plasma-mass spectrometry imaging of cisplatin-induced nephrotoxic side effects.

    PubMed

    Van Acker, Thibaut; Van Malderen, Stijn J M; Van Heerden, Marjolein; McDuffie, James Eric; Cuyckens, Filip; Vanhaecke, Frank

    2016-11-16

    Two-dimensional elemental mapping (bioimaging) via laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was performed on 5 μm thick formalin-fixed, paraffin-embedded kidney tissue sections from Cynomolgus monkeys administered with increasing pharmacological doses of cisplatin. Laterally resolved pixels of 1 μm were achieved, enabling elemental analysis on a (sub-)cellular level. Zones of high Pt response were observed in the renal cortex, where proximal tubules are present, the epithelium of which is responsible for partial reabsorption of cisplatin. Histopathological evaluation, of hematoxylin and eosin-stained serial sections, adjacent to the sections probed via LA-ICP-MS, revealed minimal to mild cisplatin-related lesions (<100 μm) in the renal cortex. Necrotic proximal tubules with sloughed epithelial cells in their lumen could be linked directly to the areas with the highest accumulation of cisplatin, indicating a direct link between cellular concentration and toxicity, thereby providing more insight into the mechanisms through which renal damage occurs.

  5. Analysis of glass fragments by laser ablation-inductively coupled plasma-mass spectrometry and principal component analysis.

    PubMed

    Bajic, Stanley J; Aeschliman, David B; Saetveit, Nathan J; Baldwin, David P; Houk, R S

    2005-09-01

    Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is used to differentiate glass samples with similar optical and physical properties based on trace elemental composition. Laser ablation increases the number of elements that can be used for differentiation by eliminating problems commonly associated with dissolution and contamination. In this study, standard residential window and tempered glass samples that could not be differentiated by refractive index or density were successfully differentiated by LA-ICP-MS. The primary analysis approach used is Principal Component Analysis (PCA) of the complete mass spectrum. PCA, a multivariate analysis technique, provides rapid analysis of samples without time-consuming pair-wise comparison of calibrated analyses or prior knowledge of the elements present in the samples. Probabilities for positive association of the individual samples are derived from PCA. Utilization of the Q-statistic with PCA allowed us to distinguish all samples within the set to a certainty greater than the 99% confidence interval.

  6. Multivariate optimization of photochemical vapor generation for direct determination of arsenic in seawater by inductively coupled plasma mass spectrometry.

    PubMed

    Gao, Ying; Sturgeon, Ralph E; Mester, Zoltán; Hou, Xiandeng; Yang, Lu

    2015-12-11

    Photochemical vapor generation (PVG) sample introduction coupled to inductively coupled plasma mass spectrometry (ICPMS) is described for the determination of As in seawater. A Plackett-Burman design (PBD) and central composite design (CCD) were employed to evaluate the significance of experimental variables relevant to the optimization of PVG-ICPMS detection. The impact of the saline matrix on the suppression of analyte signal was eliminated by use of a mixture of 20% (v/v) formic and 20% acetic acid (v/v) as the photochemical reductants. Optimized conditions yielded equivalent PVG generation efficiencies for As(III), As(V), monomethylarsonic acids (MMAs) and dimethylarsinic acids (DMAs), permitting direct and rapid determination of total arsenic in seawater without any other sample pre-treatment. Quantitation was accomplished using one point gravimetric standard addition along with a spike of (82)Se internal standard to compensate for signal drift and fluctuation during analysis. The resulting method detection limit of 3 pg g(-1) (3σ) provided a 15-fold improvement over that obtained using direct solution nebulization, and is comparable to that for conventional chemical hydride generation (HG)-ICPMS. Accuracy was demonstrated by analysis of two Certified Reference Materials (NASS-6 and CASS-5 seawater) with satisfying results characterized by precisions of 3.5% and 3.2% RSD for CASS-5 and NASS-6, respectively. Crown Copyright © 2015. Published by Elsevier B.V. All rights reserved.

  7. [Determination of iodine and its species in plant samples using ion chromatography-inductively coupled plasma mass spectrometry].

    PubMed

    Lin, Li; Chen, Guang; Chen, Yuhong

    2011-07-01

    A method was established for the determination of iodine and its species in plant samples using ion chromatography-inductively coupled plasma mass spectrometry (IC-ICP/ MS). Alkaline extraction and IC-ICP/MS were applied as the sample pre-treatment method and the detection technique respectively, for iodate and iodide determination. Moreover, high-temperature pyrolysis absorption was adopted as the pre-treatment method for total iodine analysis, which finally converted all the iodine species into iodide and measured the iodide by IC-ICP/MS. The recoveries of iodine for alkaline extraction and high-temperature pyrolysis absorption were 89.6%-97.5% and 95.2%-111.2%, respectively. The results were satisfactory. The detection limit of iodine was 0.010 mg/kg. The iodine and its speciation contents in several kinds of plant samples such as seaweeds, kelp, cabbage, tea leaf and spinach were investigated. It was shown that the iodine in seaweeds mainly existed as organic iodine; while the ones in kelp, cabbage, tea leaf and spinach mainly existed as inorganic iodine.

  8. [Progress in combination of gel electrophoresis and laser ablation inductively coupled plasma mass spectrometry for trace elements determination in proteins].

    PubMed

    Wang, Ying; Guo, Yan-li; Yuan, Hong-lin; Wei, Yong-feng; Yan, Hong-tao; Chen, Hui-hui

    2012-01-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has become a very efficient and sensitive trace, ultratrace, and surface analytical technique for the in situ study of the concentration and distribution of the elements in life sciences with high spatial resolution. It is being used more and more frequently in biological, medical materials and protein research, which will lead to a better understanding of physiology and pathology process in cells and tissues. The present review mainly introduces the strategies of combination of gel electrophoresis (GE) with LA-ICP-MS for the quantification of trace elements in proteins, including the proteins separation, elements detection and calibration methods. The paper emphasizes the basic conditions of the proteins separation, focusing on the stability of proteins during GE and the treatment methods of staining and drying of the gel to enable successful detection of the elements by LA-ICP-MS. In addition, the application of GE-LA-ICP-MS in phosphoproteins, selenoproteins and metal-binding proteins is introduced in detail. The prospects and challenge for this technique are discussed as well for further study.

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

    NASA Astrophysics Data System (ADS)

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

    2007-10-01

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

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

    PubMed

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

    2015-06-16

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

  11. Speciation of trace elements in human serum by micro anion exchange chromatography coupled with inductively coupled plasma mass spectrometry.

    PubMed

    Malavolta, Marco; Piacenza, Francesco; Basso, Andrea; Giacconi, Robertina; Costarelli, Laura; Pierpaoli, Sara; Mocchegiani, Eugenio

    2012-02-01

    Speciation analysis of essential trace elements in human serum provides important information on nutritional status and homeostatic mechanisms regulating transport processes, acute phase reactions, and protection against oxidative damage. Anion exchange high-performance liquid chromatography (HPLC) combined with inductively coupled plasma mass spectrometry (ICP-MS) has proved to be a useful tool in speciation. Here we describe a fast method that can be applied to carry out the speciation of Fe, Cu, Zn, and Se in as little as 1 microl [corrected] of serum. The method employs monolithic anion exchange micro columns installed on a tandem HPLC system coupled on-line with an ICP-MS detector. The chromatographic separation is similar to those reported previously but with considerable gain in terms of time and sample requirement. Reproducibility is acceptable for most species. Using our method, we were able to find species-specific differences between different commercially available trace element reference materials. Because the method chosen to collect blood might interfere with speciation, the proposed methodology was used to compare heparinized plasma, ethylenediaminetetraacetic acid (EDTA) plasma, and serum from adult healthy volunteers. As expected, EDTA strongly affects speciation analysis (especially for Fe and Zn), whereas changes due to the use of lithium-heparin (Li-He) as anticoagulant appear to be minimized.

  12. Characterization of the elemental composition of newborn blood spots using sector-field inductively coupled plasma-mass spectrometry

    PubMed Central

    Langer, Erica K.; Johnson, Kimberly J.; Shafer, Martin M.; Gorski, Patrick; Overdier, Joel; Musselman, Jessica; Ross, Julie A.

    2010-01-01

    We developed extraction and analysis protocols for element detection in neonatal blood spots (NBSs) using sector-field inductively coupled plasma-mass spectrometry (SF-ICP-MS). A 5% (v/v) nitric acid element extraction protocol was optimized and used to simultaneously measure 28 elements in NBS card filter paper and 150 NBSs. NBS element concentrations were corrected for filter paper background contributions estimated from measurements in samples obtained from either unspotted or spotted NBS cards. A lower 95% uncertainty limit (UL) that accounted for ICP-MS method, filter paper element concentration, and element recovery uncertainties was calculated by standard methods for each individual’s NBS element concentration. Filter paper median element levels were highly variable within and between lots for most elements. After accounting for measurement uncertainties, 11 elements (Ca, Cs, Cu, Fe, K, Mg, Na, P, Rb, S, Zn) had lower 95% ULs >0 ng/spot with estimated concentrations ranging from 0.05->50,000 ng/spot in ≥50% of NBS samples in both correction methods. In a NBS sample minority, Li, Cd, Cs, Cr, Ni, Mo, and Pb had estimated concentrations ≥20-fold higher than the respective median level. Taking measurement uncertainties into account, this assay could be used for semiquantitative newborn blood element measurement and for detection of individuals exposed to supraphysiologic levels of some trace elements. Adequate control of filter paper element contributions remains the primary obstacle to fully quantitative element measurement in newborn blood using NBSs. PMID:20588324

  13. Analysis of four toxic metals in a single rice seed by matrix solid phase dispersion -inductively coupled plasma mass spectrometry

    PubMed Central

    He, Xiufen; Chen, Lixia; Chen, Xin; Yu, Huamei; Peng, Lixu; Han, Bingjun

    2016-01-01

    Toxic metals in rice pose great risks to human health. Metal bioaccumulation in rice grains is a criterion of breeding. Rice breeding requires a sensitive method to determine metal content in single rice grains to assist the variety selection. In the present study, four toxic metals of arsenic (As), cadmium (Cd), chromium (Cr) and lead (Pb) in a single rice grain were determined by a simple and rapid method. The developed method is based on matrix solid phase dispersion using multi-wall carbon nanotubes (MWCNTs) as dispersing agent and analyzed by inductively coupled plasma mass spectrometry. The experimental parameters were systematically investigated. The limits of detection (LOD) were 5.0, 0.6, 10 and 2.1 ng g−1 for As, Cd, Cr, and Pb, respectively, with relative standard deviations (n = 6) of <7.7%, demonstrating the good sensitivity and precision of the method. The results of 30 real world rice samples analyzed by this method agreed well with those obtained by the standard microwave digestion. The amount of sample required was reduced approximately 100 fold in comparison with the microwave digestion. The method has a high application potential for other sample matrices and elements with high sensitivity and sample throughput. PMID:27922088

  14. Determination of some rare earth elements in seawater by inductively coupled plasma mass spectrometry using flow injection preconcentration

    NASA Astrophysics Data System (ADS)

    Vicente, O.; Padró, A.; Martinez, L.; Olsina, R.; Marchevsky, E.

    1998-08-01

    An on-line Eu, Tb, Ho, Tm and Lu preconcentration and determination system implemented with inductively coupled plasma mass spectrometry (ICP-MS) associated to a flow injection (FI) method was studied. Quinolin-8-ol and Amberlite XAD-7 were used for the retention of Eu, Tb, Ho, Tm and Lu, at pH 10.0. The rare earth elements were re-extracted from the microcolumn with nitric acid. The values of detection limits (DL) obtained for the preconcentration of 100 ml of aqueous solution of Eu, Tb, Ho, Tm and Lu were 0.016, 0.0023, 0.0017, 0.0035 and 0.0015 pg ml -1, respectively, with a relative standard deviation (RSD) of about 2.0%. The calibration graphs obtained by using the preconcentration system for Eu, Tb, Ho, Tm and Lu were linear at levels near the detection limits up to at least 1 ng ml -1. The method was succesfully applied to the determination of Eu, Tb, Ho, Tm and Lu in seawater samples.

  15. Determination of lanthanides in rock samples by inductively coupled plasma mass spectrometry using thorium as oxide and hydroxide correction standard

    NASA Astrophysics Data System (ADS)

    Raut, Narendra M.; Huang, Li-Shing; Aggarwal, Suresh K.; Lin, King-Chuen

    2003-05-01

    Determination of lanthanides by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) using modified mathematical correction method has been studied. Normally, the ICP-MS analysis of middle and heavier lanthanides becomes difficult by severe spectroscopic overlap of M +, MO + or MOH + ions from lighter lanthanides and Ba. A correction method based on a single element oxide yield measurement, is a simple approach to correct for the above spectroscopic overlaps. But the uncertainty in the oxide and hydroxide yields measurement of lanthanides and barium over a long period of time can lead to inaccurate results even under fixed plasma conditions. To correct this, thorium was adopted as an oxide and hydroxide correction standard. Using a ratio of lanthanide oxide yield to thorium oxide yield, the lanthanide correction factors (LCF) were established and incorporated in the mathematical correction scheme. The same factors were also established for hydroxide correction. The proposed modified correction scheme was applied to the determination of lanthanides by ICP-MS from the USGS Standard Rock samples AGV-1 and G-2. The results are in good agreement with the reported values. The method also proved to be useful in isotopic ratio measurement of lanthanides having severe isobaric overlaps.

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

    PubMed Central

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

    2015-01-01

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

  17. Determination of Pd, Rh, Pt, Au in road dust by electrothermal vaporization inductively coupled plasma mass spectrometry with slurry sampling.

    PubMed

    Hsu, Wan-Hsuan; Jiang, Shiuh-Jen; Sahayam, A C

    2013-09-10

    Inductively coupled plasma mass spectrometry coupled with ultrasonic slurry sampling electrothermal vaporization (USS-ETV-ICP-MS) has been applied to determine Pd, Rh, Pt and Au in 0.5% m/v slurries of several road dust samples. 2% m/v ammonium pyrrolidine dithiocarbamate (APDC) was used as the modifier to enhance the ion count. The influence of instrument operating conditions, slurry preparation and interferences on the ion count was reported. This method has been applied to the determination of Pd, Rh, Pt and Au in BCR 723 Road Dust and NIST SRM 2709 San Joaquin Soil reference materials and two road dust samples collected locally. The analysis results of the standard reference materials agreed with the certified values. Precision between sample replicates was better than 10% for all the determinations. The method detection limits estimated from standard addition curves were 0.9, 0.4, 0.6 and 0.4ngg(-1) for Pd, Rh, Pt and Au, respectively, in original dust samples. Copyright © 2013. Published by Elsevier B.V.

  18. Determination of antimony compounds in waters and juices using ion chromatography-inductively coupled plasma mass spectrometry.

    PubMed

    Lin, Ya-An; Jiang, Shiuh-Jen; Sahayam, A C

    2017-09-01

    A method was developed by coupling ion chromatography (IC) and inductively coupled plasma mass spectrometry (ICP-MS) for the speciation of antimony. In this study, antimony species such as antimonite [Sb(III)], antimonate [Sb(V)] and trimethyl antimony(V) (TMeSb) were separated in less than 8min using anion exchange chromatography with a Hamilton PRP-X100 column as the stationary phase. Mobile phase A was 20mmolL(-1) ethylenediaminetetraacetic acid (EDTA), 2mmolL(-1) potassium hydrogen phthalate (KHP) in 1% v/v methanol (pH 5.5) and 20mmolL(-1) EDTA, 2mmolL(-1) KHP, 40mmolL(-1) (NH4)2CO3 in 1% v/v methanol (pH 9.0) formed mobile phase B. Detection limits and relative standard deviations (RSD) were 0.012-0.032ngmL(-1) and 2.2-2.8% respectively. This method was applied to bottled waters and fruit juices purchased in Kaohsiung, Taiwan. In water samples, Sb(V) was the major species where as in juices organometallic Sb species were also present. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. [Determination of trace impurities in high purity titanium dioxide by high resolution inductively coupled plasma mass spectrometry].

    PubMed

    He, Xiao-Mei; Xie, Hua-Lin; Nie, Xi-Du; Tang, You-Gen

    2007-06-01

    An analytical method using high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) for the rapid simultaneous determination of twenty six elements (Be, Na, Mg, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Mo, Cd, Sn, Sb, Ba, Ce, Nd, Sm, Pt, Pb and Bi) in high purity titanium dioxide was described. Samples were decomposed by (NH4)2SO4 and H2SO4. Most of the spectral interferences could be avoided by measuring in the high-resolution mode. The matrix effects due to the presence of excess sulfuric acid and Ti were evaluated. The optimum conditions for the determination were tested and discussed. The standard addition method was employed for quantitative analysis. The detection limits are 0.004-0.63 microg x g(-1), the recovery ratio is 87.6%-106.4%, and the RSD is less than 3.5%. The method is accurate, quick and convenient. It has been applied to the determination of trace impurities in high purity titanium dioxide with satisfactory results.

  20. Determination of mercurial species in fish by inductively coupled plasma mass spectrometry with anion exchange chromatographic separation.

    PubMed

    Chen, Xiaopan; Han, Chao; Cheng, Heyong; Liu, Jinhua; Xu, Zigang; Yin, Xuefeng

    2013-09-24

    This work demonstrated the feasibility of mercury speciation analysis by anion exchange chromatographic separation with inductively coupled plasma mass spectrometry detection. For the first time, by complexing with the mobile phase containing 3-mercapto-1-propanesulfonate into negatively charged complexes, fast separation of inorganic mercury (Hg(2+)), monomethylmercury (MeHg), ethylmercury (EtHg) and phenylmercury (PhHg) was achieved within 5 min on a 12.5-mm strong anion exchange column. The detection limits for Hg(2+), MeHg, EtHg and PhHg were 0.008, 0.024, 0.029 and 0.034 μg L(-1), respectively. The relative standard deviations of peak height and peak area (5.0 μg L(-1) for each Hg species) were all below 3%. The determined contents of Hg(2+), MeHg and total Hg in a certified reference material of fish tissue by the proposed method were in good accordance with the certified values with satisfactory recoveries. The relative errors for determining MeHg and total mercury were -2.4% and -1.2%, respectively, with an acceptable range for spike recoveries of 94-101%. Mercury speciation in 11 fish samples were then analyzed after the pretreated procedure. The mercury contents in all fish samples analyzed were found compliant with the criteria of the National Standards of China.

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

    SciTech Connect

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

    2013-07-14

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

  2. Analysis of four toxic metals in a single rice seed by matrix solid phase dispersion -inductively coupled plasma mass spectrometry.

    PubMed

    He, Xiufen; Chen, Lixia; Chen, Xin; Yu, Huamei; Peng, Lixu; Han, Bingjun

    2016-12-06

    Toxic metals in rice pose great risks to human health. Metal bioaccumulation in rice grains is a criterion of breeding. Rice breeding requires a sensitive method to determine metal content in single rice grains to assist the variety selection. In the present study, four toxic metals of arsenic (As), cadmium (Cd), chromium (Cr) and lead (Pb) in a single rice grain were determined by a simple and rapid method. The developed method is based on matrix solid phase dispersion using multi-wall carbon nanotubes (MWCNTs) as dispersing agent and analyzed by inductively coupled plasma mass spectrometry. The experimental parameters were systematically investigated. The limits of detection (LOD) were 5.0, 0.6, 10 and 2.1 ng g(-1) for As, Cd, Cr, and Pb, respectively, with relative standard deviations (n = 6) of <7.7%, demonstrating the good sensitivity and precision of the method. The results of 30 real world rice samples analyzed by this method agreed well with those obtained by the standard microwave digestion. The amount of sample required was reduced approximately 100 fold in comparison with the microwave digestion. The method has a high application potential for other sample matrices and elements with high sensitivity and sample throughput.

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

    PubMed Central

    Dehelean, Adriana; Magdas, Dana Alina

    2013-01-01

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

  4. Green and Fast Laser Fusion Technique for Bulk Silicate Rock Analysis by Laser Ablation-Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Zhang, Chenxi; Hu, Zhaochu; Zhang, Wen; Liu, Yongsheng; Zong, Keqing; Li, Ming; Chen, Haihong; Hu, Shenghong

    2016-10-18

    Sample preparation of whole-rock powders is the major limitation for their accurate and precise elemental analysis by laser ablation inductively-coupled plasma mass spectrometry (ICPMS). In this study, a green, efficient, and simplified fusion technique using a high energy infrared laser was developed for major and trace elemental analysis. Fusion takes only tens of milliseconds for each sample. Compared to the pressed pellet sample preparation, the analytical precision of the developed laser fusion technique is higher by an order of magnitude for most elements in granodiorite GSP-2. Analytical results obtained for five USGS reference materials (ranging from mafic to intermediate to felsic) using the laser fusion technique generally agree with recommended values with discrepancies of less than 10% for most elements. However, high losses (20-70%) of highly volatile elements (Zn and Pb) and the transition metal Cu are observed. The achieved precision is within 5% for major elements and within 15% for most trace elements. Direct laser fusion of rock powders is a green and notably simple method to obtain homogeneous samples, which will significantly accelerate the application of laser ablation ICPMS for whole-rock sample analysis.

  5. Determination of (107)Pd in Pd Recovered by Laser-Induced Photoreduction with Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Asai, Shiho; Yomogida, Takumi; Saeki, Morihisa; Ohba, Hironori; Hanzawa, Yukiko; Horita, Takuma; Kitatsuji, Yoshihiro

    2016-12-20

    Safety evaluation of a radioactive waste repository requires credible activity estimates confirmed by actual measurements. A long-lived radionuclide, (107)Pd, which can be found in radioactive wastes, is one of the difficult-to-measure nuclides and results in a deficit in experimentally determined contents. In this study, a precipitation-based separation method has been developed for the determination of (107)Pd with inductively coupled plasma mass spectrometry. The photoreduction induced by pulsed laser irradiation at 355 nm provides short-time and one-step recovery of Pd. The proposed method was verified by applying it to a spent nuclear fuel sample. To recover Pd efficiently, a natural Pd standard was employed as the Pd carrier. Taking advantage of the absence of (102)Pd in spent nuclear fuel, (102)Pd in the Pd carrier was utilized as the internal standard. The chemical yield of Pd was about 90% with virtually no impurities, allowing accurate quantification of (107)Pd. The amount of (107)Pd in the Pd precipitate was 17.3 ± 0.7 ng, equivalent to 239 ± 9 ng per mg of (238)U in the sample.

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

    PubMed

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

    2017-01-22

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

  7. 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.

  8. Estimation of honey authenticity by multielements characteristics using inductively coupled plasma-mass spectrometry (ICP-MS) combined with chemometrics.

    PubMed

    Chudzinska, M; Baralkiewicz, D

    2010-01-01

    In our study the mineral content of 55 honey samples, which represented three different types of honey: honeydew, buckwheat and rape honey from different areas in Poland, was evaluated. Determination of 13 elements (Al, B, Ba, Ca, Cd, Cu, K, Mg, Mn, Na, Ni, Pb, Zn) was performed using inductively coupled plasma-mass spectrometry. We tried to prove that the analysis of quality and quantity of honey elements could be used to define honey origin by using ICP-MS as a technique for simultaneous determination of elements. Chemometric methods, such as CA and PCA, were applied to classify honey according to mineral content. CA showed three clusters corresponding to the three botanical origins of honey. PCA permitted the reduction of 13 variables to four principal components explaining 77.19% of the total variance. The first most important principal component was strongly associated with the value of K, Al, Ni and Cd. This study revealed that CA and PCA analysis appear useful tools for differentiation of honey samples authenticity using the profile of mineral content and they highlighted the relationship between the elements distribution and honey type.

  9. Slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry for the determination of As and Se in soil and sludge.

    PubMed

    Tseng, Yen-Jia; Liu, Chung-Chang; Jiang, Shiuh-Jen

    2007-04-11

    Slurry sampling electrothermal vaporization (ETV) inductively coupled plasma mass spectrometry (ICP-MS) has been applied to determine As and Se in soil and sludge samples. The influences of instrument operating conditions and slurry preparation on the ion signals were reported. Pd and ascorbic acid were used as mixed modifiers to enhance the ion signals. The effectiveness of ETV sample introduction technique for alleviating various spectral interferences in ICP-MS analysis has been demonstrated. This method has been applied to determine As and Se in NIST SRM 2709 San Joaquin soil reference material and NIST SRM 2781 domestic sludge reference material and a farmland soil sample collected locally. Since the sensitivities of As and Se in slurry solution and aqueous solution were different, analyte addition technique was used to determine As and Se in these samples. The As and Se analysis results of the reference materials agreed with the certified values. The precision between sample replicates was better than 5% for all determinations. The method detection limit estimated from analyte addition curves was about 0.03 and 0.02 microg g(-1) for As and Se, respectively, in original soil and sludge samples.

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

    NASA Astrophysics Data System (ADS)

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

    1998-10-01

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

  11. Multielemental analysis of purpleback flying squad using high resolution inductively coupled plasma-mass spectrometry (HR ICP-MS).

    PubMed

    Ichihashi, H; Kohno, H; Kannan, K; Tsumura, A; Yamasaki, S I

    2001-08-01

    Forty-four elements were analyzed in 21 tissues of purpleback flying squid, Sthenoteuthis oualaniensis, by high resolution inductively coupled plasma-mass spectrometry (HR ICP-MS) and inductively coupled plasma atomic emission spectrophotometry (ICP-AES). Greater concentrations of V, Fe, Co, Ni, Cu, Ag, Cd, Pb, and Bi were found in liver, pancreas, and ink sac than in other tissues. Ink sac concentrated remarkable levels of Ca and Sr in addition to the above-mentioned elements. Several alkalis, alkaline earth, and rare earth elements preferentially accumulated in muscle. Among the hard tissues, accumulation of V and U in beak, Ni, Zn, and Cd in gladius and Cr in skin was prominent. K, Rb, Cs, Pb, Bi and some transition elements (V, Co, Cu, Zn, Ag, Cd) were significantly (p < 0.05) higher in the livers of adult than in juvenile squids. Sodium, alkaline earth, and rare earth elements were higher in the livers of juveniles than in adult squids.

  12. Trace element analysis of extraterrestrial metal samples by inductively coupled plasma mass spectrometry: the standard solutions and digesting acids.

    PubMed

    Wang, Guiqin; Wu, Yangsiqian; Lin, Yangting

    2016-02-28

    Nearly 99% of the total content of extraterrestrial metals is composed of Fe and Ni, but with greatly variable trace element contents. The accuracy obtained in the inductively coupled plasma mass spectrometry (ICP-MS) analysis of solutions of these samples can be significantly influenced by matrix contents, polyatomic ion interference, and the concentrations of external standard solutions. An ICP-MS instrument (X Series 2) was used to determine 30 standard solutions with different concentrations of trace elements, and different matrix contents. Based on these measurements, the matrix effects were determined. Three iron meteorites were dissolved separately in aqua regia and HNO3. Deviations due to variation of matrix contents in the external standard solutions were evaluated and the analysis results of the two digestion methods for iron meteorites were assessed. Our results show obvious deviations due to unmatched matrix contents in the external standard solutions. Furthermore, discrepancy in the measurement of some elements was found between the sample solutions prepared with aqua regia and HNO3, due to loss of chloride during sample preparation and/or incomplete digestion of highly siderophile elements in iron meteorites. An accurate ICP-MS analysis method for extraterrestrial metal samples has been established using external standard solutions with matched matrix contents and digesting the samples with HNO3 and aqua regia. Using the data from this work, the Mundrabilla iron meteorite previously classified as IAB-ung is reclassified as IAB-MG. Copyright © 2016 John Wiley & Sons, Ltd.

  13. Laser ablation inductively coupled plasma mass spectrometry: a new tool for trace element analysis in ice cores.

    PubMed

    Reinhardt, H; Kriews, M; Miller, H; Schrems, O; Lüdke, C; Hoffmann, E; Skole, J

    2001-07-01

    A new method for the detection of trace elements in polar ice cores using laser ablation with subsequent inductively coupled plasma mass spectrometry analysis is described. To enable direct analysis of frozen ice samples a special laser ablation chamber was constructed. Direct analysis reduces the risk of contamination. The defined removal of material from the ice surface by means of a laser beam leads to higher spatial resolution (300-1000 microm) in comparison to investigations with molten ice samples. This is helpful for the detection of element signatures in annual layers of ice cores. The method was applied to the successful determination of traces for the elements Mg, Al, Fe, Zn, Cd, Pb, some rare-earth elements (REE) and minor constituents such as Ca and Na in ice cores. These selected elements serve as tracer elements for certain sources and their element signatures detected in polar ice cores can give hints to climate changes in the past. We report results from measurements of frozen ice samples, the achievable signal intensities, standard deviations and calibration graphs as well as the first signal progression of 205Pb in an 8,000-year-old ice core sample from Greenland. In addition, the first picture of a crater on an ice surface burnt by an IR laser made by cryogenic scanning electron microscopy is presented.

  14. 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.

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

    PubMed

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

    2007-10-17

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

  16. Characterization of silver nanoparticles using flow-field flow fractionation interfaced to inductively coupled plasma mass spectrometry.

    PubMed

    Poda, A R; Bednar, A J; Kennedy, A J; Harmon, A; Hull, M; Mitrano, D M; Ranville, J F; Steevens, J

    2011-07-08

    The ability to detect and identify the physiochemical form of contaminants in the environment is important for degradation, fate and transport, and toxicity studies. This is particularly true of nanomaterials that exist as discrete particles rather than dissolved or sorbed contaminant molecules in the environment. Nanoparticles will tend to agglomerate or dissolve, based on solution chemistry, which will drastically affect their environmental properties. The current study investigates the use of field flow fractionation (FFF) interfaced to inductively coupled plasma-mass spectrometry (ICP-MS) as a sensitive and selective method for detection and characterization of silver nanoparticles. Transmission electron microscopy (TEM) is used to verify the morphology and primary particle size and size distribution of precisely engineered silver nanoparticles. Subsequently, the hydrodynamic size measurements by FFF are compared to dynamic light scattering (DLS) to verify the accuracy of the size determination. Additionally, the sensitivity of the ICP-MS detector is demonstrated by fractionation of μg/L concentrations of mixed silver nanoparticle standards. The technique has been applied to nanoparticle suspensions prior to use in toxicity studies, and post-exposure biological tissue analysis. Silver nanoparticles extracted from tissues of the sediment-dwelling, freshwater oligochaete Lumbriculus variegatus increased in size from approximately 31-46nm, indicating a significant change in the nanoparticle characteristics during exposure.

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

    SciTech Connect

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

    2009-12-01

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

  18. Complexation of europium and uranium by humic acids analyzed by capillary electrophoresis-inductively coupled plasma mass spectrometry.

    PubMed

    Möser, Christina; Kautenburger, Ralf; Philipp Beck, Horst

    2012-05-01

    Investigations of the mobility of radioactive and nonradioactive substances in the environment are important tasks for the development of a future disposal in deep geological formations. Dissolved organic matter (DOM) can play an important role in the mobilization of metal ions due to complexation. In this study, we investigate the complexation behavior of humic acid (HA) as a model substance for DOM and its influence on the migration of europium as homologue for the actinide americium and uranium as the principal component of nuclear fuel. As speciation technique, capillary electrophoresis (CE) was hyphenated with inductively coupled plasma mass spectrometry (ICP-MS). For the study, 0.5 mg·L⁻¹ of the metals and 25 mg·L⁻¹ of (purified Aldrich) HA and an aqueous solution sodium-perchlorate with an ionic strength of 10 mM at pH 5 were used. CE-ICP-MS clearly shows the different speciation of the triple positively charged europium and the double positively charged uranyl cation with HA. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

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

  20. [Determination of 33 inorganic elements in human hair by electricity plate digestion and inductively coupled plasma-mass spectrometry].

    PubMed

    Luo, Ru-Xin; Ma, Dong; Zhang, Su-Jing; Zhuo, Xian-Yi

    2013-12-01

    To establish the electricity plate digestion and inductively coupled plasma-mass spectrometry (ICP-MS) method for determination of 33 inorganic elements in human hair. Lithium (6Li), Germanium (72Ge), Yttrium (89Y), Indium (115In), and Terbium (159Tb) were used as internal standards. The electric heating board digestion in a mixture of nitric acid and hydrogen peroxide was used as the pre-treatment of the hair. Thirty-three inorganic elements in human hair were analyzed by ICP-MS method. The detection limit of ICP-MS was 0.0001 microg/g(Th)-10.9 microg/g (Ca) and the limit of quantitation was 0.0005 microg/g (Th)-25 microg/g (Ca). The recovery rate of this method was 86%-113%. The RSD for the intra-day and inter-day were less than 9.2%. The method was not statistically different from microwave digestion method. This method is highly efficient and accurate. It can be used for analysis of 33 inorganic elements in human hair.

  1. Simultaneous sample preconcentration and matrix removal using field-flow fractionation coupled to inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Al-Ammar, Assad; Siripinyanond, Atitaya; Barnes, Ramon M.

    2001-10-01

    An on-channel sample preconcentration-matrix removal arrangement, based on coupling field-flow fractionation (FFF) to inductively coupled plasma mass spectrometry (ICP-MS), has been constructed for on-line sample pretreatment ICP-MS trace element determination. A commercial FFF system is modified to incorporate an on-channel preconcentration procedure allowing injection of up to 50 ml of sample, which could be preconcentrated by 50-1400 fold. A high molecular weight complexing agent added to the sample forms strong complexes with the measured trace analytes but not with the sample matrix. When the sample-complexing agent mixture is introduced to the FFF unit, the uncomplexed matrix element is removed by permeation through a membrane that separates the FFF sample compartment. The trace analytes remain in the FFF channel, because their high molecular weight complexes do not permeate through the membrane. Preconcentration and matrix elimination occur simultaneously. The matrix-free, preconcentrated sample is introduced directly to the ICP-MS nebulizer. The method was tested using 10-ml sample aliquots that contain As, Cd, Cu, Mo, Pb, Re, Sn, Te, Tl, Y, Zn and Zr analytes and 5000 mg l -1 Ca or Na matrices and ethylene imine polymer complexing agent. Copper and Re isotopic ratio values in reference standards also were determined after preconcentration and matrix element removal.

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

    PubMed

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

    2013-11-15

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

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

    PubMed

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

    2004-12-01

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

  4. Direct determination of arsenic in fresh and saline waters by electrothermal vaporization inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Conrad Grégoire, D.; de Lourdes Ballinas, Maria

    1997-01-01

    A method is described for the direct determination of arsenic in fresh and saline waters by electrothermal vaporization inductively coupled plasma mass spectrometry. Arsenic could be determined directly in waters containing up to 10 000 μg ml -1 NaCl without interference from the formation of 75ArCl +. For non-saline waters, arsenic was determined directly with the addition to both aqueous calibration standards and samples of 0.1 μg each of Pd and Mg to act as physical carriers. For the analysis of highly saline waters, the use of Pd and Mg chemical modifier served to thermally stabilize arsenic up to a temperature of 1000°C, while the separate addition of 8 mg of ammonium nitrate was used to remove chloride from the sample. This eliminated serious spectral interference on 75As + from 75ArCl +. Although the ArCl + spectral interference was completely eliminated, residual Na co-volatilized with As caused signal suppression, requiring the use of the method of standard additions for calibration. An absolute limit of detection limit for As of 0.069 pg was obtained corresponding to 6.9 pg ml -1 in a 10 μl sample.

  5. Complexation studies with lanthanides and humic acid analyzed by ultrafiltration and capillary electrophoresis-inductively coupled plasma mass spectrometry.

    PubMed

    Kautenburger, Ralf; Beck, Horst Philipp

    2007-08-03

    For the long-term storage of radioactive waste, detailed information about geo-chemical behavior of radioactive and toxic metal ions under environmental conditions is necessary. Humic acid (HA) can play an important role in the immobilisation or mobilisation of metal ions due to complexation and colloid formation. Therefore, we investigate the complexation behavior of HA and its influence on the migration or retardation of selected lanthanides (europium and gadolinium as homologues of the actinides americium and curium). Two independent speciation techniques, ultrafiltration and capillary electrophoresis coupled with inductively coupled plasma mass spectrometry (CE-ICP-MS) have been compared for the study of Eu and Gd interaction with (purified Aldrich) HA. The degree of complexation of Eu and Gd in 25 mg l(-1) Aldrich HA solutions was determined with a broad range of metal loading (Eu and Gd total concentration between 10(-6) and 10(-4) mol l(-1)), ionic strength of 10 mM (NaClO4) and different pH-values. From the CE-ICP-MS electropherograms, additional information on the charge of the Eu species was obtained by the use of 1-bromopropane as neutral marker. To detect HA in the ICP-MS and separate between HA complexed and non complexed metal ions in the CE-ICP-MS, we have halogenated the HA with iodine as ICP-MS marker.

  6. Determination of platinum originating from carboplatin in human urine and canine excretion products by inductively coupled plasma mass spectrometry.

    PubMed

    Janssens, Tine; Brouwers, Elke E M; de Vos, Johan P; Schellens, Jan H M; Beijnen, Jos H

    2011-04-01

    We present highly sensitive, rapid methods for the determination of Pt originating from carboplatin in human urine and canine urine, feces, and oral fluid. The methods are based on the quantification of Pt by inductively coupled plasma mass spectrometry, and allow quantification of 7.50 ng/L Pt in human and canine urine (in 15 μL of matrix), 15.0 ng/L Pt in canine oral fluid (in 15 μL of matrix), and 0.105 ng/g Pt in canine feces (in 5 μg of matrix). Sample pretreatment mainly involved dilution with appropriate diluents. The performance of the methods fulfilled the most recent FDA guidelines for bioanalytical method validation. Validated ranges of quantification were 7.50 to 1.00 × 10(4) ng/L Pt in human and canine urine, 0.105-30.0 ng/g Pt in canine feces, and 15.0 to 1.00 × 10(4) ng/L Pt in canine oral fluid. Canine urine and oral fluid cannot be easily obtained. Therefore, we also investigated the validity of the usage of human matrix samples for the preparation of calibration standards and quality control samples as alternatives, to be used in future clinical studies. The assays are used to support biomonitoring studies and pharmacokinetic studies in pet dogs treated with carboplatin.

  7. Molecularly imprinted polymers as selective adsorbents for ambient plasma mass spectrometry.

    PubMed

    Cegłowski, Michał; Smoluch, Marek; Reszke, Edward; Silberring, Jerzy; Schroeder, Grzegorz

    2017-05-01

    The application of molecularly imprinted polymers (MIPs) as molecular scavengers for ambient plasma ionization mass spectrometry has been reported for the first time. MIPs were synthesized using methacrylic acid as functional monomer; nicotine, propyphenazone, or methylparaben as templates; ethylene glycol dimethacrylate as a cross-linker; and 2,2'-azobisisobutyronitrile as polymerization initiator. To perform ambient plasma ionization experiments, a setup consisting of the heated crucible, a flowing atmospheric-pressure afterglow (FAPA) plasma ion source, and a quadrupole ion trap mass spectrometer has been used. The heated crucible with programmable temperature allows for desorption of the analytes from MIPs structure which results in their direct introduction into the ion stream. Limits of detection, linearity of the proposed analytical procedure, and selectivities have been determined for three analytes: nicotine, propyphenazone, and methylparaben. The analytes used were chosen from various classes of organic compounds to show the feasibility of the analytical procedure. The limits of detections (LODs) were 10 nM, 10, and 0.5 μM for nicotine, propyphenazone, and methylparaben, respectively. In comparison with the measurements performed for the non-imprinted polymers, the values of LODs were improved for at least one order of magnitude due to preconcentration of the sample and reduction of background noise, contributing to signal suppression. The described procedure has shown linearity in a broad range of concentrations. The overall time of single analysis is short and requires ca. 5 min. The developed technique was applied for the determination of nicotine, propyphenazone, and methylparaben in spiked real-life samples, with recovery of 94.6-98.4%. The proposed method is rapid, sensitive, and accurate which provides a new option for the detection of small organic compounds in various samples. Graphical abstract The experimental setup used for analysis.

  8. Time-resolved measurements with single droplet introduction to investigate space-charge effects in plasma mass spectrometry.

    PubMed

    Stewart, I I; Olesik, J W

    1999-02-01

    An investigation of the space-charge induced effects of high concentrations of Pb+ matrix ions on Li+ analyte ions in inductively coupled plasma mass spectrometry (ICP-MS) is presented using a vertically oriented mass spectrometer with single droplet introduction. Greater reproducibility and stability in droplet-to-droplet sample introduction using the monodisperse microparticulate injector (MDMI) was achieved with the vertical orientation. Typical variation (%RSD) in the droplet-to-droplet arrival times, and mass spectrometry peak analytical areas are better than 5%. With this precision, a more quantitative description of the space-charge effect on a single cloud of ions is obtained. Both radial and axial space-charge effects were found to occur in the ion beam. Radial effects result in a loss in intensity because of poor transmission or collisions at surfaces within the mass spectrometer. Axial effects modify the kinetic energy distribution of background ion beam components (e.g., 16O+ and 40Ar+) and sampled ion cloud constituents (e.g., 7Li+). However, axial effects do not appear to generate significant broadening of sampled ion clouds within the mass spectrometer. At the point of charge separation and high ion-beam charge density, the ion cloud maxima for Li and Pb are not coincident. This is because of mass dependent diffusion in the ICP as the ion clouds approach the sampling orifice. Space-charge induced ion loss occurs predominantly at a localized region after the Li+ sampled cloud peak maximum. When the Pb concentration in the sample is sufficiently high the 7Li+ sampled signal has a bimodal peak shape. The existence of the dip and its relative location in the bimodal 7Li+ sampled signal suggests that space-charge effects are localized to the region of high charge density occurring just after charge separation.

  9. Determination of low-level plutonium in seawater by sector field inductively coupled plasma mass spectrometry: method validation.

    PubMed

    Vassileva, Emilia; Han, Eunmi; Levy, Isabelle

    2017-03-01

    Sources of plutonium isotopes to the marine environment are well defined, both spatially and temporally which makes plutonium (Pu) a potential tracer for oceanic processes. This paper presents the optimisation and validation of an analytical procedure for ultra-trace determination of Pu isotopes ((239)Pu and (240)Pu) in seawater based on the external calibration and sector field inductively coupled plasma mass spectrometry (SF ICP-MS) determination. Additionally, method for Pu isotope ratio ((240)Pu/(239)Pu) in marine samples is also discussed. A combination of two-step anion exchange (AG1-X8) and one-step extraction chromatography (TEVA) was very efficient resulting in uranium (U) decontamination factor of 5 × 10(6)-1 × 10(8). A full validation approach in line with ISO 17025 standard and Eurachem guidelines was followed. With this in mind, blanks, recovery (87 ± 8 %, k = 2), within-laboratory repeatability (5.6 %), limits of detection (0.12 and 0.08 fg mL(-1) for (239)Pu and (240)Pu, respectively) and expanded uncertainty (13 %, k = 2) were systematically assessed. The procedure was applied for the determination of (239)Pu and Pu in seawater sample coming from Mediterranean Sea. Obtained results were in good agreement with results obtained with alpha spectrometry, applied on the same seawater sample. Pu/(239)Pu atom ratio in seawater sample from the Mediterranean Sea was also determined. The precision and accuracy of (240)Pu/(239)Pu isotopic ratio analysis were carefully examined using NBS-947 isotopic standard. (240)Pu/(239)Pu ratio was found to be 0.187 ± 0.006 and is in agreement with accepted ratios for the global fallout of Pu.

  10. Trace element biomonitoring in hair of school children from a polluted area by sector field inductively coupled plasma mass spectrometry.

    PubMed

    Drobyshev, Evgenii J; Solovyev, Nikolay D; Ivanenko, Natalya B; Kombarova, Maria Yu; Ganeev, Alexander A

    2017-01-01

    In the current study, a biomonitoring of 18 hair trace elements (Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Ni, Pb, Se, V, Zn, Ca, Na and P) in school children from Leningradskaya Oblast' is reported. A case group, residing in a proximity to the toxic waste disposal grounds (Krasniy Bor), has been assessed vs. controls from a non-urban settlement Seltso. In total, 166 hair samples were analysed using double focusing sector field inductively coupled plasma mass spectrometry after microwave-assisted sample digestion with nitric acid. For the determination of Ca, Na and P inductively coupled plasma optical emission spectrometry was employed. For the validation, a reference material and spiked hair samples were analysed. The data obtained was processed using parametric statistics and factor analysis. Determined concentrations of trace elements were in agreement with the previously published results on chemically polluted areas. In the case group, linear correlations between Al, Cr, Cu, Fe, Ni and V were observed. Also, these metals correlated to selenium hair content in the case group. Additionally, a correlation between hair Se and P was observed in the case subjects. Several gender differences in trace content were observed within each group. However, no age- or body index-related difference was found. The obtained results show that closely located waste disposal grounds intensifies trace element exposure in school children of Krasniy Bor. However, judging from rather high values for the controls, total environmental status of the region seems to be unstable, so additional monitoring and chemical safety measures are required. Copyright © 2016 Elsevier GmbH. All rights reserved.

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

    PubMed

    Tanaka, Kazuya; Takahashi, Yoshio; Shimizu, Hiroshi

    2007-02-05

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

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

    PubMed Central

    Pappas, R. Steven

    2015-01-01

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

  13. An overview of recent applications of inductively coupled plasma-mass spectrometry (ICP-MS) in determination of inorganic impurities in drugs and pharmaceuticals.

    PubMed

    Nageswara Rao, R; Talluri, M V N Kumar

    2007-01-04

    The recent applications of inductively coupled plasma-mass spectrometry (ICP-MS) in determination of trace level inorganic impurities in drugs and pharmaceuticals have been reviewed. ICP-MS coupled with LC, GC and CE was used for speciation of heavy metals in pharmaceutical products. The review covers the period from 1995 to 2005 during which the technique was applied not only for determination of metallic impurities but also the assay of various trace elements in pharmaceuticals.

  14. An argon-nitrogen-hydrogen mixed-gas plasma as a robust ionization source for inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Makonnen, Yoseif; Beauchemin, Diane

    2014-09-01

    Multivariate optimization of an argon-nitrogen-hydrogen mixed-gas plasma for minimum matrix effects, while maintaining analyte sensitivity as much as possible, was carried out in inductively coupled plasma mass spectrometry. In the presence of 0.1 M Na, the 33.9 ± 3.9% (n = 13 elements) analyte signal suppression on average observed in an all-argon plasma was alleviated with the optimized mixed-gas plasma, the average being - 4.0 ± 8.8%, with enhancement in several cases. An addition of 2.3% v/v N2 in the outer plasma gas, and 0.50% v/v H2 to the central channel, as a sheath around the nebulizer gas flow, was sufficient for this drastic increase in robustness. It also reduced the background from ArO+ and Ar2+ as well as oxide levels by over an order of magnitude. On the other hand, the background from NO+ and ArN+ increased by up to an order of magnitude while the levels of doubly-charged ions increased to 7% (versus 2.7% in an argon plasma optimized for sensitivity). Furthermore, detection limits were generally degraded by 5 to 15 fold when using the mixed-gas plasma versus the argon plasma for matrix-free solution (although they were better for several elements in 0.1 M Na). Nonetheless, the drastically increased robustness allowed the direct quantitative multielement analysis of certified ore reference materials, as well as the determination of Mo and Cd in seawater, without using any matrix-matching or internal standardization.

  15. Separation, Sizing, and Quantitation of Engineered Nanoparticles in an Organism Model Using Inductively Coupled Plasma Mass Spectrometry and Image Analysis.

    PubMed

    Johnson, Monique E; Hanna, Shannon K; Montoro Bustos, Antonio R; Sims, Christopher M; Elliott, Lindsay C C; Lingayat, Akshay; Johnston, Adrian C; Nikoobakht, Babak; Elliott, John T; Holbrook, R David; Scott, Keana C K; Murphy, Karen E; Petersen, Elijah J; Yu, Lee L; Nelson, Bryant C

    2017-01-24

    For environmental studies assessing uptake of orally ingested engineered nanoparticles (ENPs), a key step in ensuring accurate quantification of ingested ENPs is efficient separation of the organism from ENPs that are either nonspecifically adsorbed to the organism and/or suspended in the dispersion following exposure. Here, we measure the uptake of 30 and 60 nm gold nanoparticles (AuNPs) by the nematode, Caenorhabditis elegans, using a sucrose density gradient centrifugation protocol to remove noningested AuNPs. Both conventional inductively coupled plasma mass spectrometry (ICP-MS) and single particle (sp)ICP-MS are utilized to measure the total mass and size distribution, respectively, of ingested AuNPs. Scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDS) imaging confirmed that traditional nematode washing procedures were ineffective at removing excess suspended and/or adsorbed AuNPs after exposure. Water rinsing procedures had AuNP removal efficiencies ranging from 57 to 97% and 22 to 83%, while the sucrose density gradient procedure had removal efficiencies of 100 and 93 to 98%, respectively, for the 30 and 60 nm AuNP exposure conditions. Quantification of total Au uptake was performed following acidic digestion of nonexposed and Au-exposed nematodes, whereas an alkaline digestion procedure was optimized for the liberation of ingested AuNPs for spICP-MS characterization. Size distributions and particle number concentrations were determined for AuNPs ingested by nematodes with corresponding confirmation of nematode uptake via high-pressure freezing/freeze substitution resin preparation and large-area SEM imaging. Methods for the separation and in vivo quantification of ENPs in multicellular organisms will facilitate robust studies of ENP uptake, biotransformation, and hazard assessment in the environment.

  16. Determination of mercury in coal by isotope dilution cold-vapor generation inductively coupled plasma mass spectrometry.

    PubMed

    Long, Stephen E; Kelly, W Robert

    2002-04-01

    A method based on isotope dilution cold-vapor inductively coupled plasma mass spectrometry (ID-CV-ICPMS) has been developed for high-accuracy determinations of mercury in bituminous and sub-bituminous coals. A closed-system digestion process employing a Carius tube is used to completely oxidize the coal matrix and chemically equilibrate the mercury in the sample with a 201Hg isotopic spike. The digestates are diluted with high-purity quartz-distilled water, and the mercury is released as a vapor by reduction with tin(II) chloride. Measurements of 201Hg/202Hg isotope ratios are made using a quadrupole ICPMS system in time-resolved analysis mode. The new method has some significant advantages over existing methods. The instrument detection limit is less than 1 pg/mL. The average blank (n = 17) is 30 pg, which is roughly 1 order of magnitude lower than the equivalent microwave digestion procedure. The detection limit in coal is blank limited and is approximately 40 pg/g. Memory effects are very low. The relative reproducibility of the analytical measurements is approximately 0.5% for mercury concentrations in the range 10-150 ng/g. The method has been used to measure mercury concentrations in six coal reference materials, SRM 1632b (77.4 ng/g), SRM 1632c (94.3 ng/g), BCR 40 (433.2 ng/g), BCR 180 (125.0 ng/g), BCR 181 (135.8 ng/g), and SARM 20 (252.6 ng/g), as well as a coal fly ash, SRM 1633b (143.1 ng/g). The method is equally applicable to other types of fossil fuels including both crude and refined oils.

  17. [Determination of trace elements in cigarette flavours by closed-vessel microwave digestion-inductively coupled plasma mass spectrometry].

    PubMed

    Li, Li; Wu, Zhi-Ying; Zhu, Feng-Peng; Li, Dong-Liang; Dai, Ya; Hu, Qing-Yuan; Tang, Gang-Ling

    2010-12-01

    Tobacco flavours have great effect on the aroma, taste and quality stabilization of cigarettes. In order to effectively control the quality of cigarette flavours and reduce the content level of toxic elements in cigarette mainstream smoke, a method for the simultaneous determination of Be, V, Cr, Mn, Ni, Cu, Zn, As, Se, Sr, Mo, Cd, Tl and Pb in cigarette flavours by inductively coupled plasma mass spectrometry (ICP-MS) with closed-vessel microwave assisted digestion was developed. The linear correlative coefficients for all elements are better than 0.999 4 and the precision of measurement ranges from 1.3% to 9.5% in terms of relative standard deviation (n = 5). The recoveries for the cigarette flavour samples and the limits of detection are in the range of 88.1%-109.3% and 0.003-0.13 microg x L(-1), respectively. The results of experiment show that the method can meet the requirements of trace analysis. Thirty eight cigarette flavours from different cigarette manufacturing enterprises were determined. The results indicate that: (1) the contents of Be, Tl, Mo, Cd, V, Pb and As in cigarette flavours are very lower, the average values of which are all lower than 0.1 microg x g(-1). The content levels of Mn, Zn and Sr in cigarette flavours are higher, and that of other 4 elements are moderate. (2) The content difference of Mn, Cd and Sr in different cigarette flavours is usually bigger, the coefficients of variation of which are 276.4%, 238.7% and 243.8%, respectively.

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

    NASA Astrophysics Data System (ADS)

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

    2005-04-01

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

  19. Total arsenic determination and speciation in infant food products by ion chromatography-inductively coupled plasma-mass spectrometry.

    PubMed

    Vela, Nohora P; Heitkemper, Douglas T

    2004-01-01

    Health risk associated with dietary arsenic intake may be different for infants and adults. Seafood is the main contributor to arsenic intake for adults while terrestrial-based food is the primary source for infants. Processed infant food products such as rice-based cereals, mixed rice/formula cereals, milk-based infant formula, applesauce and puree of peaches, pears, carrots, sweet potatoes, green beans, and squash were evaluated for total and speciated arsenic content. Arsenic concentrations found in rice-based cereals (63-320 ng/g dry weight) were similar to those reported for raw rice. Results for the analysis of powdered infant formula by inductively coupled plasma-mass spectrometry (ICP-MS) indicated a narrow and low arsenic concentration range (12 to 17 ng/g). Arsenic content in puree infant food products, including rice cereals, fruits, and vegetables, varies from <1 to 24 ng/g wet weight. Sample treatment with trifluoroacetic acid at 100 degrees C were an efficient and mild method for extraction of arsenic species present in different food matrixes as compared to alternative methods that included sonication and accelerated solvent extraction. Extraction recoveries from 94 to 128% were obtained when the summation of species was compared to total arsenic. The ion chromatography (IC)-ICP-MS method selected for arsenic speciation allowed for the quantitative determination of inorganic arsenic [As(III) + As(V)], dimethylarsinic acid (DMA), and methylarsonic acid (MMA). Inorganic arsenic and DMA are the main species found in rice-based and mixed rice/formula cereals, although traces of MMA were also detected. Inorganic arsenic was present in freeze-dried sweet potatoes, carrots, green beans, and peaches. MMA and DMA were not detected in these samples. Arsenic species in squash, pears, and applesauce were not detected above the method detection limit [5 ng/g dry weight for As(III), MMA, and DMA and 10 ng/g dry weight for As(V)].

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

    NASA Technical Reports Server (NTRS)

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

    2003-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2006-11-01

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

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

    PubMed

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

    2010-09-01

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

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

    USGS Publications Warehouse

    Rusk, Brian; Koenig, Alan; Lowers, Heather

    2011-01-01

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

  4. Speciation of gadolinium in surface water samples and plants by hydrophilic interaction chromatography hyphenated with inductively coupled plasma mass spectrometry.

    PubMed

    Lindner, Uwe; Lingott, Jana; Richter, Silke; Jakubowski, Norbert; Panne, Ulrich

    2013-02-01

    Hydrophilic interaction chromatography (HILIC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) was optimized for speciation analysis of gadolinium-based contrast agents in environmental samples, in particular surface river waters and plants. Surface water samples from the Teltow channel, near Berlin, were investigated over a distance of 5 km downstream from the influx of a wastewater treatment plant. The total concentration of gadolinium increased significantly from 50 to 990 ng L(-1) due to the influx of the contrast agents. After complete mixing with the river water, the concentration remained constant over a distance of at least 4 km. Two main substances [Dotarem(®) (Gd-DOTA) and Gadovist(®) (Gd-BT-DO3A)] have been identified in the river water using standards. A gadolinium-based contrast agent, possibly Gd-DOTA (Dotarem(®)), was also detected in water plant samples taken from the Teltow channel. Therefore, uptake of contrast agents [Gadovist(®) (Gd-BTDO3A), Magnevist(®) (Gd-DTPA), Omniscan(®) (Gd-DTPA-BMA), Dotarem(®) (Gd-DOTA), and Multihance(®) (Gd-BOPTA)] by plants was investigated in a model experiment using Lepidium sativum (cress plants). HILIC-ICP-MS was used for identification of different contrast agents, and a first approach for quantification using aqueous standard solutions was tested. For speciation analysis, all investigated contrast agents could be extracted from the plant tissues with a recovery of about 54 % for Multihance(®) (Gd-BOPTA) up to 106 % for Gadovist(®) (Gd-BT-DO3A). These experiments demonstrate that all contrast agents investigated are transported from the roots to the leaves where the highest content was measured.

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

    NASA Astrophysics Data System (ADS)

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

    2007-01-01

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

  6. Speciation of cisplatin in environmental water samples by hydrophilic interaction liquid chromatography coupled to inductively coupled plasma mass spectrometry.

    PubMed

    Vidmar, Janja; Martinčič, Anže; Milačič, Radmila; Ščančar, Janez

    2015-06-01

    Cisplatin is still widely used for treatment of numerous types of tumours. Different speciation methods have been applied to study behaviour of the intact drug and its individual biotransformation species in various clinical samples. These methods are mainly based on electrophoresis, size exclusion (SEC) or ion chromatography (IC) techniques coupled to inductively coupled plasma mass spectrometry (ICP-MS). Hydrophilic interaction liquid chromatography (HILIC), which is a common technique for separation of polar substances, was rarely applied for separation of cisplatin and its hydrolysed metabolites. There is also a lack of information available on the occurrence of cisplatin and its hydrolysed complexes in the environmental waters. In the present study the concentrations of Pt were determined in hospital wastewaters by ICP-MS. A procedure for separation of cisplatin and its aqueous hydrolysed complexes by the use of HILIC column was optimized. Quantification of separated Pt species was performed by isotope dilution (ID)-ICP-MS procedure. Low limits of detection (LODs) and quantification (LOQs) were obtained for cisplatin and its hydrolysed complexes ranging from 0.0273 to 0.1726 ng Pt/mL and from 0.0909 to 0.5753 ng Pt/mL, respectively. Good repeatability of the procedure with relative standard deviation (RSD) lower than ±2.3% was obtained. The column recoveries, which ranged from 95 to 101%, indicated that the procedure developed enabled quantitative speciation analysis of aqueous cisplatin complexes. The ZIC-HILIC-ID-ICP-MS procedure was successfully applied in speciation of cisplatin in spiked hospital wastewater samples.

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

    PubMed

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

    2010-12-01

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

  8. Studies on Mixed-Gas Plasmas and Segmented Flow Injection for Use with Inductively Coupled Plasma Mass Spectrometry.

    NASA Astrophysics Data System (ADS)

    Craig, Jane Mary

    In this thesis, mixed gas plasmas and flow injection into air bubbles were investigated for use with inductively coupled plasma mass spectrometry (ICP-MS), in order to improve the technique's analytical capabilities. The mixed gas plasmas were created in two different ways: (i) by adding another gas, either argon, nitrogen, or hydrogen, to the nebulizer gas flow using a sheathing device or (ii) by adding nitrogen to the plasma gas flow. The introduction of each sheathing gas led to degraded analyte sensitivity but generally improved plasma stability, resulting in improved detection limits for a few elements. Introduction of nitrogen into the plasma gas, under the same operating conditions used for an all-argon plasma, resulted in degraded sensitivity but improved signal-to-noise and signal-to-background ratios for Cr, Fe, and Se. The tolerance of ICP-MS to effects caused by the concomitant elements Na and K was improved by addition of nitrogen to the plasma gas flow. Flow injection using a segmented air/water carrier resulted in improved precision, sensitivity, and detection limits compared to those obtained using an all-water carrier. The enhancement in sensitivity was found to be mass dependent and was attributable to more than simply a reduction in dispersion. Under optimized operating conditions, using segmented flow injection resulted in similar or improved detection limits for all analytes except Se when compared to those obtained using continuous nebulization. Changing the gas used to segment the carrier stream did not result in appreciable changes in analyte signals or positions of maximum ionization within the plasma, indicating that the fundamental properties of the plasma did not change. The tolerance of ICP-MS to effects caused by the concomitant elements Na and Ca was not improved by using a segmented carrier compared to that experienced using an all-water carrier.

  9. Determination of rare earth elements in environmental matrices by sector-field inductively coupled plasma mass spectrometry.

    PubMed

    Riondato, J; Vanhaecke, F; Moens, L; Dams, R

    2001-07-01

    In the framework of an international certification campaign, sector-field inductively coupled plasma mass spectrometry (sector-field ICP-MS) was used for the accurate determination of the rare earth elements in five candidate reference materials: aquatic plant, calcareous soil, mussel tissue, river sediment, and tuna muscle. All samples were taken into solution by use of microwave-assisted or mixed microwave-assisted / open beaker acid digestion. Subsequently, the samples were appropriately diluted and subjected to ICP-MS analysis. Except for Sc, all the elements involved were determined at low mass resolution (R = 300). For Sc, application of a higher resolution setting (R = 3,000) was required to separate the analyte signal from those of several molecular ions which gave rise to spectral overlap at low mass resolution. Some of the heavier REE can also suffer from spectral overlap attributed to the occurrence of oxide ions (MO+) of the lighter REE and Ba. This spectral overlap could be successfully overcome by mathematical correction. Matrix effects were overcome by use of two carefully selected internal standards, such that external calibration could be used. On each occasion, a geological reference material was analyzed as a quality-control sample and the reliability of all results obtained was additionally checked by means of chondrite normalization. For tuna muscle the content of all REE was below the limit of detection. For calcareous soil and river sediment, low to sub microg g(-1) values were observed, whereas the REE content of aquatic plant and mussel tissue was considerably lower (low to sub ng g(-1)). Overall, the results obtained were in excellent agreement with the average values, calculated on the basis of all "accepted" values, obtained in different laboratories using different techniques.

  10. Microwave digestion methods for the determination of trace elements in brain and liver samples by inductively coupled plasma mass spectrometry.

    PubMed

    Krachler, M; Radner, H; Irgolic, K J

    1996-05-01

    Two microwave digestion systems (open-focused and closed-pressurized) were tested for the mineralization of human brain and bovine liver (NIST SRM 1577a) as dissolution steps prior to the determination of 16 trace elements (Bi, Cd, Co, Cs, Cu, Fe, Hg, Mn, Mo, Pb, Rb, Sb, Sn, Sr, Tl, and Zn) by inductively coupled plasma mass spectrometry (ICP-MS). Digestion parameters (mass of sample, digestion mixture, and power/time steps) were optimized using temperature and pressure sensors. Digestions with the open-focused microwave system require larger volumes of conc. HNO(3) and 30% H(2)O(2) than digestions with the closed-pressurized system. Both systems produce correct results for the bovine liver samples. The concentrations obtained for the digests of the open-focused system tend to be less precise than the concentrations from the "closed-pressurized" digests. Because the "open-focused" digests must be diluted to 50 mL to bring the acid concentration to 0.7-2.0 mol/L required by the ICP-MS (closed-pressurized digests need to be diluted to only 20 mL), the detection limits for the system with the open-focused digestion are higher than for the system with the closed-pressurized digestor. The open-focused digestor cannot handle more than 150 mg brain tissue, whereas the closed-pressurized system can mineralize 470 mg. The latter method gave better results with brain tissue than the open-focused system. The preparation of brain tissue as reference material for the determination of trace elements in brain samples is described.

  11. Optimization of plasma sampling depth and aerosol gas flow rates for single particle inductively coupled plasma mass spectrometry analysis.

    PubMed

    Kálomista, Ildikó; Kéri, Albert; Galbács, Gábor

    2017-09-01

    We performed experiments to assess the separate and also the combined effect of the sampling depth and the aerosol gas flow rates on the signal formation in single particle inductively coupled plasma mass spectrometry (spICP-MS) measurements by using dispersions containing Ag and Au NPs. It was found that the NP signal can significantly be improved by the optimization of the sampling depth. With respect to the "robust" setting, a signal improvement of nearly 100% could be achieved, which translates into a 25-30% improvement in size detection limits. It was also found that the shape of the spICP-MS signal histograms also change with the change of the plasma sampling depth. It was demonstrated that nanoparticle peak separation can also be significantly enhanced by using sampling depth optimization. The effect of the aerosol dilution gas flow, now standard in most ICP-MS instruments, on the spICP-MS signal formation was also studied for the first time in the literature, as this flow was hoped to make spICP-MS measurements more practical and faster via the on-line dilution of the aerosol generated from nano-dispersions. Our experimental results revealed that the dilution gas flow can only be used for a moderate aerosol dilution in spICP-MS measurements, if the gas flow going to the pneumatic nebulizer is proportionally lowered at the same time. This however was found to cause a significant worsening in the operation of the sample introduction system, which gives rise to a strong NP signal loss. Thus it was concluded that the use of the aerosol dilution gas flow, in its present form, can not be suggested for spICP-MS analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Hypoxia-Responsive Cobalt Complexes in Tumor Spheroids: Laser Ablation Inductively Coupled Plasma Mass Spectrometry and Magnetic Resonance Imaging Studies.

    PubMed

    O'Neill, Edward S; Kaur, Amandeep; Bishop, David P; Shishmarev, Dmitry; Kuchel, Philip W; Grieve, Stuart M; Figtree, Gemma A; Renfrew, Anna K; Bonnitcha, Paul D; New, Elizabeth J

    2017-08-21

    Dense tumors are resistant to conventional chemotherapies due to the unique tumor microenvironment characterized by hypoxic regions that promote cellular dormancy. Bioreductive drugs that are activated in response to this hypoxic environment are an attractive strategy for therapy with anticipated lower harmful side effects in normoxic healthy tissue. Cobalt bioreductive pro-drugs that selectively release toxic payloads upon reduction in hypoxic cells have shown great promise as anticancer agents. However, the bioreductive response in the tumor microenvironment must be better understood, as current techniques for monitoring bioreduction to Co(II) such as X-ray absorption near-edge structure and extended X-ray absorption fine structure provide limited information on speciation and require synchrotron radiation sources. Here, we present magnetic resonance imaging (MRI) as an accessible and powerful technique to monitor bioreduction by treating the cobalt complex as an MRI contrast agent and monitoring the change in water signal induced by reduction from diamagnetic Co(III) to paramagnetic Co(II). Cobalt pro-drugs built upon the tris(2-pyridylmethyl)amine ligand scaffold with varying charge were investigated for distribution and activity in a 3D tumor spheroid model by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and MRI. In addition, paramagnetic (1)H NMR spectroscopy of spheroids enabled determination of the speciation of activated Co(II)TPAx complexes. This study demonstrates the utility of MRI and associated spectroscopy techniques for understanding bioreductive cobalt pro-drugs in the tumor microenvironment and has broader implications for monitoring paramagnetic metal-based therapies.

  13. Elimination of suction effect in interfacing microchip electrophoresis with inductively coupled plasma mass spectrometry using porous monolithic plugs.

    PubMed

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

    2012-07-07

    A suction-free interfacing method was developed for microchip electrophoresis hyphenated with inductively coupled plasma mass spectrometry (MCE-ICP-MS). The hyphenated system was composed of a microchip, a demountable capillary microflow nebulizer (d-CMN) combined with a heated single pass spray chamber, a negative pressure sampling device, a high voltage power supply, a syringe pump and an ICP-MS. To eliminate the nebulizer suction generated by the pneumatic nebulizer and to ensure that the makeup solution flowed into the nebulizer, two porous polymer plugs were fabricated in the microchip. As a result, reasonably true electropherograms were obtained when compared to the CE separation performed in the traditional MCE-ICP-MS mode without porous polymer plugs. Electrophoretic separation of I(-) and IO(3)(-) was achieved within 25 s in a microchip with an effective separation length of only 15 mm at an electric field of 857 V cm(-1) using 10 mmol L(-1) borate (pH 9.2) as the running buffer. A resolution of 1.3 was obtained and the absolute detection limits for I(-) and IO(3)(-) were 0.12 and 0.13 fg, respectively. The precisions (RSD, n = 10) of the migration time and peak height for I(-) and IO(3)(-) were in the range of 1.1-1.6% and 2.5-2.8%, respectively. Two table salt samples were analyzed by an external calibration method. The iodate contents were in accordance with their labeled values. The recoveries of I(-) and IO(3)(-) in the table salt samples were in the range of 92-105%.

  14. [Determination of five arsenic species in rice by liquid chromatography-inductively coupled plasma-mass spectrometry].

    PubMed

    Gong, Jiadi; Cao, Xiaolin; Cao, Zhaoyun; Bian, Yingfang; Yu, Shasha; Chen, Mingxue

    2014-07-01

    A method was developed for the simultaneous determination of arsenic acid [As (V)], arsenious acid [As (III)], arsenobetaine (AsB), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) in rice by liquid chromatography-inductively coupled plasma-mass spectrometry (LC-ICP-MS). The extraction reagent was 0.3 mol/L nitric acid with heat-assistant condition for 1.5 h at 95 degrees C. Then, the five arsenic species were separated by an anion exchange column (Dionex IonPac AS19, 250 mm x 4 mm) and detected by ICP-MS. Four kinds of extracted solutions were compared through the extraction efficiency. The concentration of nitric acid, the temperature and the extraction time were optimized. The recoveries of the five arsenic species spiked in rice at two levels ranged from 89.6% to 99.5% with the relative standard deviations (RSDs, n = 5) of 0.6% - 3.6%. The measured values of the arsenic species in standard rice materials were consistent with their standard values. The linear ranges were 0.05 - 200 microg/L for AsB and DMA, 0.10-400 microg/L for As (III) and MMA, 0.15-600 microg/L for As (V). The limits of detection for the five arsenic species were 0.15-0.45 microg/kg. The results showed that the method is much more precise for the risk assessment of the rice. This method is simple, accurate and durable for the determination of arsenic species in rice.

  15. Discrimination of side-window glass of Korean autos by laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Lee, Sin-Woo; Ryu, Jong-Sik; Min, Ji-Sook; Choi, Man-Yong; Lee, Kwang-Sik; Shin, Woo-Jin

    2016-07-15

    Fragments of glass from cars are often found at crime scenes and can be crucial evidence for solving the crime. The glass fragments are important as trace evidence at crime scenes related to car accidents and burgled homes. By identifying the origin of glass fragments, it is possible to infer the identity of a suspect. Our results represent a promising approach to a thorough forensic investigation of car glass. Thirty-five samples from the side windows of cars produced and used in South Korea were collected from the official agencies of five car manufacturers and from two glassmakers. In addition, 120 samples from side mirrors were collected from the same suppliers as well as from small businesses. Their chemical compositions (including Pb isotopes) were analyzed using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and linear discriminant analysis (LDA) was performed. The percentages of major elements (Si, Ca, and Fe) in side-window glass varied within narrow ranges (30.0 ± 2.36%, 5.93 ± 0.52%, and 0.33 ± 0.05%, respectively), while the differences among Pb isotope ratios were not significant. In contrast, light rare earth elements (LREEs) were different from each glassmaker. From the LDA, the types of side-window glass were successfully discriminated according to car manufacturer, glassmaker, and even glass thickness. However, glass from side mirrors cannot be used for good forensic identifiers. Discrimination techniques for side-window glass, although not for side mirrors, using chemical compositions combined with multivariate statistical analyses provide evidence for forensic investigations. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  16. Comparison of laser ablation-inductively coupled plasma-mass spectrometry and micro-X-ray fluorescence spectrometry for elemental imaging in Daphnia magna.

    PubMed

    Gholap, Deepti S; Izmer, Andrei; De Samber, Björn; van Elteren, Johannes T; Selih, Vid S; Evens, Roel; De Schamphelaere, Karel; Janssen, Colin; Balcaen, Lieve; Lindemann, Inge; Vincze, Laszlo; Vanhaecke, Frank

    2010-04-01

    Visualization of elemental distributions in thin sections of biological tissue is gaining importance in many disciplines of biological and medical research. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and scanning micro-X-ray fluorescence spectrometry (micro-XRF) are two widely used microanalytical techniques for elemental mapping. This article compares the capabilities of the two techniques for imaging the distribution of selected elements in the model organism Daphnia magna in terms of detection power and spatial resolution. Sections with a thickness of 10 and 20 microm of the fresh water crustacean Daphnia magna were subjected to LA-ICP-MS and micro-XRF analysis. The elemental distributions obtained for Ca, P, S and Zn allow element-to-tissue correlation. LA-ICP-MS and micro-XRF offer similar limits of detection for the elements Ca and P and thus, allow a cross-validation of the imaging results. LA-ICP-MS was particularly sensitive for determining Zn (LOD 20 microg g(-1), 15 microm spot size) in Daphnia magna, while the detection power of micro-XRF was insufficient in this context. However, LA-ICP-MS was inadequate for the measurement of the S distributions, which could be better visualized with micro-XRF (LOD 160 microg g(-1), 5 s live time). Both techniques are thus complementary in providing an exhaustive chemical profiling of tissue samples.

  17. Bioimaging of metals and biomolecules in mouse heart by laser ablation inductively coupled plasma mass spectrometry and secondary ion mass spectrometry.

    PubMed

    Becker, J Sabine; Breuer, Uwe; Hsieh, Hui-Fang; Osterholt, Tobias; Kumtabtim, Usarat; Wu, Bei; Matusch, Andreas; Caruso, Joseph A; Qin, Zhenyu

    2010-11-15

    Bioimaging mass spectrometric techniques allow direct mapping of metal and biomolecule distributions with high spatial resolution in biological tissue. In this study laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) was used for imaging of transition metals (Fe, Cu, Zn, Mn, and Ti), alkali and alkaline-earth metals (Na, K, Mg, and Ca, respectively), and selected nonmetals (such as C, P, and S) in native cryosections of mouse heart. The metal and nonmetal images clearly illustrated the shape and the anatomy of the samples. Zinc and copper were inhomogeneously distributed with average concentrations of 26 and 11 μg g(-1), respectively. Titanium and manganese were detected at concentrations reaching 1 and 2 μg g(-1), respectively. The highest regional metal concentration of 360 μg g(-1)was observed for iron in blood present in the lumen of the aorta. Secondary ion mass spectrometry (SIMS) as an elemental and biomolecular mass spectrometric technique was employed for imaging of Na, K, and selected biomolecules (e.g., phosphocholine, choline, cholesterol) in adjacent sections. Here, two different bioimaging techniques, LA-ICPMS and SIMS, were combined for the first time, yielding novel information on both elemental and biomolecular distributions.

  18. Determination of silver in nano-plastic food packaging by microwave digestion coupled with inductively coupled plasma atomic emission spectrometry or inductively coupled plasma mass spectrometry.

    PubMed

    Lin, Q-B; Li, B; Song, H; Wu, H-J

    2011-08-01

    The detection of silver in nano-plastic food packaging by microwave digestion coupled with either inductively coupled plasma atomic emission spectrometry (ICP-AES) or inductively coupled plasma mass spectrometry (ICP-MS) was investigated. Microwave digestion was optimised by trialling different acid mixtures. Both ICP-AES and ICP-MS showed good reproducibility, repeatability and recovery. For ICP-AES the limit of detection of the method (LODm) was 25.0 µg g(-1), the limit of detection of the instrument (LODi) was 30.0 ng ml(-1), the linear range was 0.10-10.0 µg ml(-1). The average recoveries for blank samples spiked with silver at 100, 250 and 500 µg g(-1) ranged from 82.53% to 87.60%, and the relative standard deviations (RSDs) were from 1.79% to 8.30%. For ICP-MS analysis the LODm was 0.75 µg g(-1), the LODi was 0.04 ng ml(-1), the linear range was 0.20-500.0 ng ml(-1), the RSDs were 2.26-4.79%, and the recoveries were 78.09-92.72% (spiked concentrations of 2.5, 5.0 and 10.0 µg g(-1)). These results indicate that the proposed method could be employed to analyse silver in nano-plastic food packaging.

  19. Speciation of arsenic in marine food (Anemonia sulcata) by liquid chromatography coupled to inductively coupled plasma mass spectrometry and organic mass spectrometry.

    PubMed

    Contreras-Acuña, M; García-Barrera, T; García-Sevillano, M A; Gómez-Ariza, J L

    2013-03-22

    Arsenic species have been investigated in Anemonia sulcata, which is frequently consumed food staple in Spain battered in wheat flour and fried with olive oil. Speciation in tissue extracts was carried out by anion/cation exchange chromatography with inductively coupled plasma mass spectrometry (HPLC-(AEC/CEC)-ICP-MS). Three methods for the extraction of arsenic species were investigated (ultrasonic bath, ultrasonic probe and focused microwave) and the optimal one was applied. Arsenic speciation was carried out in raw and cooked anemone and the dominant species are dimethylarsinic acid (DMA(V)) followed by arsenobetaine (AB), As(V), monomethylarsonic acid (MA(V)), tetramethylarsonium ion (TETRA) and trimethylarsine oxide (TMAO). In addition, arsenocholine (AsC), glyceryl phosphorylarsenocholine (GPAsC) and dimethylarsinothioic acid (DMAS) were identified by liquid chromatography coupled to triple quadrupole mass spectrometry (HPLC-MS). These results are interesting since GPAsC has been previously reported in marine organisms after experimental exposure to AsC, but not in natural samples. In addition, this paper reports for the first time the identification of DMAS in marine food. Copyright © 2013 Elsevier B.V. All rights reserved.

  20. Speciation analysis of inorganic tin by on-column complexation ion chromatography with inductively coupled plasma mass spectrometry and electrospray mass spectrometry.

    PubMed

    Huang, Li; Yang, Die; Guo, Xiangquan; Chen, Zuliang

    2014-11-14

    Inductively coupled plasma-mass spectrometry (ICP-MS) and electrospray mass spectrometry (ESI-MS) were used as complementary methods to identify Sn-pentaacetic acid (DTPA) complex formation. ESI-MS was used to initially confirm the formation of [Sn(DTPA)](3-) and [Sn(DTPA)](1-) and their MS spectra suggest these tin complexes were stable in solution. On-column complexation of tin with DTPA and the separation of [Sn(DTPA)](3-) and [Sn(DTPA)](1-) was performed on anion-exchange chromatography with an mobile phase containing 20mM NH4NO3 and 3mM DTPA at pH 6.0, and the subsequent detection of [Sn(DTPA)](3-) and [Sn(DTPA)](1-) was achieved by ICP-MS. Linear plots were obtained in a concentration range of 1.0-1000 μg L(-1) with detection limits ranging from 0.1 to 0.3 μg L(-1). The developed procedure allows the simultaneous determination of [Sn(DTPA)](3-) and [Sn(DTPA)](1-) in less than 5 min with a RSD between 2.1 and 2.7%. The recoveries of [Sn(DTPA)](3-) and [Sn(DTPA)](1-) were found to be 96.8 and 99.4%, respectively, when the sample was spiked with 20 μg L(-1) standard. Finally, the proposed procedure was used for the determination of tin species in contaminated water.

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

    PubMed Central

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

    2012-01-01

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

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

    PubMed

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

    2012-05-15

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

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

    SciTech Connect

    Niu, Hongsen

    1995-02-10

    The fundamental and practical aspects are described for extracting ions from atmospheric pressure plasma sources into an analytical mass spectrometer. Methodologies and basic concepts of inductively coupled plasma mass spectrometry (ICP-MS) are emphasized in the discussion, including ion source, sampling interface, supersonic expansion, slumming process, ion optics and beam focusing, and vacuum considerations. Some new developments and innovative designs are introduced. The plasma extraction process in ICP-MS was investigated by Langmuir measurements in the region between the skimmer and first ion lens. Electron temperature (Te) is in the range 2000--11000 K and changes with probe position inside an aerosol gas flow. Electron density (ne) is in the range 108--1010 -cm at the skimmer tip and drops abruptly to 106--108 cm-3 near the skimmer tip and drops abruptly to 106--108 cm-3 downstream further behind the skimmer. Electron density in the beam leaving the skimmer also depends on water loading and on the presence and mass of matrix elements. Axially resolved distributions of electron number-density and electron temperature were obtained to characterize the ion beam at a variety of plasma operating conditions. The electron density dropped by a factor of 101 along the centerline between the sampler and skimmer cones in the first stage and continued to drop by factors of 104--105 downstream of skimmer to the entrance of ion lens. The electron density in the beam expansion behind sampler cone exhibited a 1/z2 intensity fall-off (z is the axial position). An second beam expansion originated from the skimmer entrance, and the beam flow underwent with another 1/z2 fall-off behind the skimmer. Skimmer interactions play an important role in plasma extraction in the ICP-MS instrument.

  4. Characterization of silver nanoparticle aggregates using single particle-inductively coupled plasma-mass spectrometry (spICP-MS).

    PubMed

    Kim, Hyun-A; Lee, Byung-Tae; Na, So-Young; Kim, Kyoung-Woong; Ranville, James F; Kim, Soon-Oh; Jo, Eunhye; Eom, Ig-Chun

    2017-03-01

    The single particle-inductively coupled plasma-mass spectrometry was applied to characterize the aggregates of AgNPs. was applied to characterize the aggregates of AgNPs. Two sizes of citrate-AgNPs and PVP-AgNPs were used at relatively high and predicted environmental concentrations under various ionic strengths. Citrate-AgNP aggregated with increases in the ionic strength, whereas PVP-AgNPs were sterically stable. The critical coagulation concentrations were 85 mM and 100 mM NaNO3 for 60 nm and 100 nm citrate-AgNPs at 2 mg L(-1) as total Ag obtained by dynamic light scattering (DLS). At 2 mg L(-1) as total Ag, the mass of an aggregate gradually increased with increasing ionic strength for both citrate-AgNP during spICP-MS analyses. The average number of single particles derived from the mass in an aggregate was calculated to be 8.68 and 5.95 for 60 nm and 100 nm citrate-AgNPs at 85 mM and 100 mM NaNO3, respectively after 2 h. The mass fractal dimensions were determined to be 2.97 and 2.83, further implying that the aggregate structures were very rigid and compact. Only marginal increases in the average mass and number of single particles in the aggregate units were found during 24 h under environmentally relevant AgNP concentrations. The average number of single particles constituting an aggregate unit for 60 nm and 100 nm citrate-AgNPs was 1.24 and 1.37 after 24 h at a high ionic strength. These results indicate that under environmentally relevant conditions, the collision frequency is predominant in the aggregation and that NPs are likely to encounter natural colloids such as clay and organic matter to form hetero-aggregates.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

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

    USGS Publications Warehouse

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

    2008-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2005-03-01

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

  8. Analysis of magnetic elements in otoliths of the macula lagena in homing pigeons with inductively coupled plasma mass spectrometry.

    PubMed

    Zhao, Ying; Huang, Yi-Na; Shi, Lv; Chen, Lin

    2009-06-01

    The macula lagena in birds is located at the apical end of the cochlea and contains many tiny otoliths. The macula lagena is innervated and has neural projections to the brainstem, but its physiological function is still unclear. It remains disputable that it is because otoliths in the lagena are rich in elements Fe and Zn that birds can obtain geomagnetic information for homing. To clarify this issue, we carried out a study to determine whether or not otoliths in the lagena of homing pigeons are richer in magnetic elements than those in the saccule and the utricle. The contents of ferromagnetic elements (Fe, Co, Ni) and other metal elements in lagenal otoliths of adult homing pigeons were precisely analyzed with inductively coupled plasma mass spectrometry (ICP-MS) of high sensitivity, and then they were compared with those in saccular and utricular otoliths (all the contents were normalized to Ca). In adult homing pigeons, the contents of ferromagnetic elements (Fe, Co, Ni) in lagenal otoliths were less than 0.7% (normalized to Ca element) and were the same order in magnitude as those in saccular and utricular otoliths. The content of Fe in lagenal otoliths was not significantly different from that in utricular otoliths and was even lower than that in saccular otoliths. The content of Co in lagenal otoliths was lower than that in saccular otoliths and higher than that in utricular otoliths. The content of Ni in lagenal otoliths was not significantly different from that in saccular otoliths and was higher than that in utricular otoliths. The contents of other metal elements Na, Mg, K, Al, Mn and Pb in lagenal otoliths were not significantly different from those in utricular and saccular otoliths. The contents of metal elements Zn, Ba and Cu in lagenal otoliths were lower than those in saccular otoliths. The contents of magnetic elements in lagenal otoliths of homing pigeons are not much higher than those in utricular and saccular otoliths, which does not support

  9. Determination of selenium compounds in urine by high-performance liquid chromatography--inductively coupled plasma mass spectrometry.

    PubMed

    Chatterjee, Amit; Tao, Hiroaki; Shibata, Yasuyuki; Morita, Masatoshi

    2003-05-16

    Selenium species, selenite, selenate, selenomethionine (Semet), seneloethionine (Seet) and trimethylselenonium ion (TmSe) were separated in aqueous solution using a gel-permeation (polyvinyl alcohol-based resin) GS-220 column by eluting with 25 mM tetramethylammonium hydroxide and 25 mM malonic acid at pH 7.9. The GS-220 column coupled with inductively coupled plasma mass spectrometry was used for the separation, identification, and quantification of selenium compounds present in certified reference material (CRM) No. 18 human urine from the National Institute for Environmental Studies in Japan (NIES). Spiking of the authentic standard to the urine and use of a silica-based LC-SCX cation-exchange column validated the peak of selenium compounds. High concentrations of chloride and bromide in the urine eluted from the GS-220 column formed molecular ions 40Ar37Cl+ and 81Br1H+ in the plasma, and these molecular ions created additional peaks in the chromatograms when 77Se and 82Se isotopes were monitored respectively. Thus, both the isotopes were selected concurrently for signal monitoring to eliminate the interfering signals. On the LC-SCX column, chloride and bromide were eluted with selenate and complicated its determination, but the peak of TmSe was baseline separated from rest of the Se compounds. Two unknown Se compounds were detected in both the columns. An additional Se compound having the same retention time as that of Semet was detected on the LC-SCX column. Peaks of selenite, selenate, TmSe and unknown selenium compounds in the urine were baseline separated on the GS-220 column, and were free from interferences. Therefore, the GS-220 column was used for the determination of selenium compounds in NIES CRM No. 18. Unknown Se compounds were the predominant selenium species followed by selenite, TmSe and selenate. The estimated value of TmSe as Se, by the standard additions method using the GS-220 column, was 3.42 +/- 0.17 microg l(-1) and was in good agreement

  10. A multi-element ICP-MS survey method as an alternative to the heavy metals limit test for pharmaceutical materials.

    PubMed

    Wang, T; Wu, J; Hartman, R; Jia, X; Egan, R S

    2000-10-01

    A multi-element inductively coupled plasma-mass spectrometry (ICP-MS) survey method has been demonstrated as an alternative to the antiquated 'heavy metals limit test' prescribed by United States Pharmacopoeia (USP), European Pharmacopoeia (EP), and British Pharmacopoeia (BP), for drug substances, intermediates, and raw materials. The survey method is simple, fast, sensitive, semi-quantitative to quantitative, and includes all the elements which can be analyzed by atomic spectroscopy.

  11. Detection of chemical warfare agent degradation products in foods using liquid chromatography coupled to inductively coupled plasma mass spectrometry and electrospray ionization mass spectrometry.

    PubMed

    Kubachka, Kevin M; Richardson, Douglas D; Heitkemper, Douglas T; Caruso, Joseph A

    2008-08-22

    The following work presents the exploration of three chromatographic separations in combination with inductively coupled plasma mass spectrometry (ICP-MS) for the analysis of chemical warfare agent degradation products (CWADPs). The robust ionization of ICP is virtually matrix independent thus enabling the examination of sample matrices generally considered too complicated for analysis by electrospray ionization (ESI) or atmospheric pressure chemical ionization MS with little to no sample preparation. The analysis was focused on detecting CWADPs in food matrices, as they present possible vehicles for terrorist contamination. Due to the specific detection of (31)P by ICP-MS, resolution of analytes of interest from other P-containing interferences (H(3)PO(4)) was a crucial part of each separation. Up to 10 CWADPs were separated in the presence of H(3)PO(4) with detection limits in the low part per billion levels using the methods described. Additionally, one method was tailored to be compatible with both ICP-MS and ESI-MS making structural verification possible.

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

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

    PubMed

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

    2015-01-07

    The fast sequential multi-element determination of 11 elements present at different concentration levels in environmental samples and drinking waters has been investigated using high-resolution continuum source flame atomic absorption spectrometry. The main lines for Cu (324.754 nm), Zn (213.857 nm), Cd (228.802 nm), Ni (232.003 nm) and Pb (217.001 nm), main and secondary absorption lines for Mn (279.482 and 279.827 nm), Fe (248.327, 248.514 and 302.064 nm) and Ca (422.673 and 239.856 nm), secondary lines with different sensitivities for Na (589.592 and 330.237 nm) and K (769.897 and 404.414 nm) and a secondary line for Mg (202.582 nm) have been chosen to perform the analysis. A flow injection system has been used for sample introduction so sample consumption has been reduced up to less than 1 mL per element, measured in triplicate. Furthermore, the use of multiplets for Fe and the side pixel registration approach for Mg have been studied in order to reduce sensitivity and extend the linear working range. The figures of merit have been calculated and the proposed method was applied to determine these elements in a pine needles reference material (SRM 1575a), drinking and natural waters and soil extracts. Recoveries of analytes added at different concentration levels to water samples and extracts of soils were within 88-115% interval. In this way, the fast sequential multi-element determination of major and minor elements can be carried out, in triplicate, with successful results without requiring additional dilutions of samples or several different strategies for sample preparation using about 8-9 mL of sample. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Optimized microwave-assisted decomposition method for multi-element analysis of glass standard reference material and ancient glass specimens by inductively coupled plasma atomic emission spectrometry.

    PubMed

    Zachariadis, G; Dimitrakoudi, E; Anthemidis, A; Stratis, J

    2006-02-28

    A novel microwave-assisted wet-acid decomposition method for the multi-element analysis of glass samples using inductively coupled plasma atomic emission spectrometry (ICP-AES) was developed and optimized. The SRM 621 standard reference glass material was used for this purpose, because it has similar composition with either archaeological glass specimens or common modern glasses. For the main constituents of SRM 621 (Ca, Na, Al, Fe, Mg, Ba and Ti), quality control data are given for all the examined procedures. The chemical and instrumental parameters of the method were thoroughly optimized. Thirteen acid mixtures of hydrochloric, nitric, and hydrofluoric acids in relation to two different microwave programs were examined in order to establish the most efficient protocol for the determination of metals in glass matrix. For both microwave programs, an intermediate step was employed with addition of H(3)BO(3) in order to compensate the effect of HF, which was used in all protocols. The suitability of the investigated protocols was evaluated for major (Ca, Na, Al), and minor (Fe, Mg, Ba, Ti, Mn, Cu, Sb, Co, Pb) glass constituents. The analytes were determined using multi-element matrix matched standard solutions. The analytical data matrix was processed chemometrically in order to evaluate the examined protocols in terms of their accuracy, precision and sensitivity, and eventually select the most efficient method for ancient glass. ICP-AES parameters such as spectral line, RF power and sample flow rate were optimized using the proposed protocol. Finally, the optimum method was successfully applied to the analysis of a number of ancient glass fragments.

  15. Determination of size and element composition distributions of complex colloids by sedimentation field-flow fractionation—inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Murphy, Deirdre M.

    1993-01-01

    Sedimentation field-flow fractionation (SdFFF) and inductively coupled plasma mass spectrometry (ICP-MS) have been directly combined and the resulting SdFFF-ICP-MS instrument can be used to produce element based size distributions of colloidal samples. Using appropriate tracer elements the size distributions of specific components can be picked out from a complex mixture. Changes in chemical composition of mixtures as a function of particle size can be readily monitored by plotting appropriate element atomic ratio distributions. These applications have been illustrated using data obtained with samples of the clay minerals kaolinite and illite and a natural suspended particulate matter from the Darling River (Australia).

  16. Barium determination in gastric contents, blood and urine by inductively coupled plasma mass spectrometry in the case of oral barium chloride poisoning.

    PubMed

    Łukasik-Głębocka, Magdalena; Sommerfeld, Karina; Hanć, Anetta; Grzegorowski, Adam; Barałkiewicz, Danuta; Gaca, Michał; Zielińska-Psuja, Barbara

    2014-01-01

    A serious case of barium intoxication from suicidal ingestion is reported. Oral barium chloride poisoning with hypokalemia, neuromuscular and cardiac toxicity, treated with intravenous potassium supplementation and hemodialysis, was confirmed by the determination of barium concentrations in gastric contents, blood, serum and urine using the inductively coupled plasma mass spectrometry method. Barium concentrations in the analyzed specimens were 20.45 µg/L in serum, 150 µg/L in blood, 10,500 µg/L in urine and 63,500 µg/L in gastric contents. Results were compared with barium levels obtained from a non-intoxicated person.

  17. Inductively coupled plasma-mass spectrometry (ICP-MS) for quantitative analysis in environmental and life sciences: a review of challenges, solutions, and trends.

    PubMed

    Pröfrock, Daniel; Prange, Andreas

    2012-08-01

    This focal point review provides an overview of recent developments and capabilities of inductively coupled plasma mass spectrometry (ICP-MS) coupled with different separation techniques for applications in the fields of quantitative environmental and bio-analysis. Over the past years numerous technical improvements, which are highlighted in this review, have helped to promote the evolution of ICP-MS to one of the most versatile tools for elemental quantification. In particular, the benefits and possibilities of using state-of-the-art hyphenated ICP-MS approaches for quantitative analysis are demonstrated with a focus on environmental and bio-analytical applications.

  18. Speciation of selenium in a commercial dietary supplement by liquid chromatography coupled with inductively coupled plasma-mass spectrometry (ICP-MS).

    PubMed

    Ayouni, Linda; Barbier, Frédérique; Imbert, Jean-Louis; Lantéri, Pierre; Grenier-Loustalot, Marie-Florence

    2007-05-01

    Size exclusion and anion-exchange chromatographies coupled with inductively coupled plasma-mass spectrometry (ICP-MS) were used for the speciation of selenium (Se) in a dietary supplement. A sequential extraction method resulted in 85% recovery of Se and 78% of the Se extracted could be identified. The results obtained show that selenomethionine and its oxide are the predominant compounds, while selenite and selenomethylcysteine are present at low concentrations. Methane seleninic acid, probably arising from the oxidation of selenomethylcysteine, accounted for 22% of total Se. High-molecular-weight compounds, probably proteins, were detected in sodium dodecyl sulfate (SDS) and driselase extracts by size exclusion chromatography.

  19. Development of an optimised method for analysis of (90)Sr in decommissioning wastes by triple quadrupole inductively coupled plasma mass spectrometry.

    PubMed

    Russell, B; García-Miranda, M; Ivanov, P

    2017-08-01

    The ongoing development of an optimised procedure for the measurement of (90)Sr in decommissioning samples using the latest generation triple quadrupole inductively coupled plasma mass spectrometry (ICP-QQQ-MS) is presented. The procedure incorporates digestion, and separation from interferences using a combination of wet chemical and instrument-based separation using the ICP-QQQ-MS reaction cell. The key factors under study are the procedural time and limits of detection achievable compared to existing radiometric techniques. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. [The modern approaches to the determination of the content of elemental impurities in the pharmaceutical substances with the use of inductively-coupled plasma mass-spectrometry].

    PubMed

    Bol'shov, M A; Seregina, I F; Uspenskaya, E V; Titorovich, O V; Syroeshki, A V; Maksimova, T V; Pletneva, T V

    2015-01-01

    The elemental impurities contained in the composition of the pharmaceutical dose forms are known to be capable of interacting with their active substances and excipients and of catalyzing their degradation; thereby, they alter stability of the drug products and exert toxic effects on the human tissues. The present publication was designed to report the results of the purity tests for ascorbic acid, valine, and galactose substances by inductively-coupled plasma mass-spectrometry (IBP-MS). This method is recommended for use by the US and EU pharmacopoeias and for the replacement of the traditional test for heavy metals with the use of PbS ethanol suspension.

  1. Inductively coupled plasma-mass spectrometry as an element-specific detector for field-flow fractionation particle separation

    USGS Publications Warehouse

    Taylor, Howard E.; Garbarino, John R.; Murphy, Deirdre M.; Beckett, Ronald

    1992-01-01

    An inductively coupled plasma-mass spectrometer was used for the quantitative measurement of trace elements In specific,submicrometer size-fraction particulates, separated by sedimentation field-flow fractionation. Fractions were collected from the eluent of the field-flow fractionation centrifuge and nebulized, with a Babington-type pneumatic nebulizer, into an argon inductively coupled plasma-mass spectrometer. Measured Ion currents were used to quantify the major, minor, and trace element composition of the size-separated colloidal (< 1-microm diameter) particulates. The composition of surface-water suspended matter collected from the Yarra and Darling rivers in Australia is presented to illustrate the usefulness of this tool for characterizing environmental materials. An adsorption experiment was performed using cadmium lon to demonstrate the utility for studying the processes of trace metal-suspended sediment interactions and contaminant transport in natural aquatic systems.

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

    PubMed

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

    2016-02-01

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

  3. Determination of selenium in biological samples by slurry sampling-electrothermal vaporization-in situ fusion-isotope dilution-microwave-induced nitrogen plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Kawano, Takafumi; Nishide, Akifumi; Okutsu, Kentaro; Minami, Hirotsugu; Zhang, Qiangbin; Inoue, Sadanobu; Atsuya, Ikuo

    2005-03-01

    Determination of selenium in certified reference biological materials by slurry sampling electrothermal vaporization (ETV)-isotope dilution (ID)-microwave-induced nitrogen plasma mass spectrometry (MIP-MS) was performed. Several parameters such as the heating conditions were studied in order to obtain optimal conditions. A special heating stage called the in situ fusion stage was applied just before the pyrolysis stage in the electrothermal vaporization process in order to fuse the biological sample and to achieve selenium isotope-equilibration between selenium in the sample and the 78Se spike solution. The slurry sample containing an appropriate amount of biological sample, 78Se spike solution, and sodium hydroxide as an alkaline flux was injected into the electrothermal vaporization unit. The slurry sample was in situ fused, pyrolyzed, and then vaporized. The ion counts at m/ z=78 and 80, the spike and reference isotopes, respectively, could be measured accurately without interference caused by argon since nitrogen plasma was used. The analytical utility of the proposed slurry sampling-electrothermal vaporization-in situ fusion-microwave-induced nitrogen plasma mass spectrometry was evaluated by determining the selenium concentration in certified reference biological materials, and the analytical results obtained were in good agreement with the certified values. The limit of detection for selenium was 90 ng g -1. The relative standard deviation of the determination of selenium was 8-15% with a high sample throughput (less than 30 min per sample including a slurry preparation.)

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

    PubMed Central

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

    2011-01-01

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

  5. Simultaneous extraction of arsenic and selenium species from rice products by microwave-assisted enzymatic extraction and analysis by ion chromatography-inductively coupled plasma-mass spectrometry.

    PubMed

    Mar, Jorge L Guzmán; Reyes, Laura Hinojosa; Rahman, G M Mizanur; Kingston, H M Skip

    2009-04-22

    A microwave-assisted enzymatic extraction (MAEE) method was developed for the simultaneous extraction of arsenic (As) and selenium (Se) species in rice products. The total arsenic and selenium content in the enzymatic extracts were determined by inductively coupled plasma mass spectrometry (ICP-MS), while the speciation analysis was performed by ion chromatography coupled to inductively coupled plasma-mass spectrometry (IC-ICP-MS). The main factors affecting the enzymatic extraction process were evaluated in NIST SRM-1568a rice flour. The optimum extraction conditions were 500 mg of sample, 50 mg of protease XIV, and 25 mg of alpha-amylase in aqueous medium during 40 min at 37 degrees C. The extraction recoveries of total As and Se reached 100 +/- 3 and 80 +/- 4%, respectively. The species stability study during the MAEE process did not show transformation of the target species in rice products. The results of As speciation obtained for SRM-1568a were in agreement with previous studies of As speciation performed on the same reference material. The proposed method was applied to the determination of As and Se species in rice and rice-based cereals. Arsenite [As(III)], arsenate [As(V)], dimethylarsinic acid (DMA), and selenomethionine (SeMet) were the predominant species identified in rice products.

  6. Multi-element analysis of water decoction of medicine food homology plants using inductively coupled plasma-tandem mass spectrometry

    NASA Astrophysics Data System (ADS)

    Fu, Liang; Shi, Shu-Yun; Chen, Xiao-Qing

    2017-07-01

    The concentration of twelve trace elements in the water decoction of medicine food homology plants (MFHP) was determined by inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS). Water decoctions of MFHP were analyzed directly using the MS/MS mode after acidification by 1% (v/v) nitric acid. The polyatomic interferences were eliminated by oxygen mass shift, oxygen on-mass, and ammonia mass shift. The accuracy of the method was verified by analysis of standard reference materials. This method was utilized to investigate the water decoction composition of 16 common Chinese MFHPs. The trace elements in the water decoctions of different MFHPs presented significantly different dissolution ratios. The dissolution ratio of V was the lowest (4.21%-14.86%), whereas Zn showed the highest dissolution ratio (24.87%-86.80%). In addition, the dissolution ratio of heavy metallic elements in most MFHP was equal to or was lower than 30%. Therefore, consumption of MHFP decoction could decrease the heavy metal intake associated with MFHP use and reduce the risk of heavy metal poisoning.

  7. An interlaboratory comparison of bone lead measurements via K-shell X-ray fluorescence spectrometry: validation against inductively coupled plasma mass spectrometry

    PubMed Central

    Bellis, David J.; Todd, Andrew C.

    2012-01-01

    109Cd-based K-shell X-ray fluorescence spectrometry (hereafter, for brevity, XRF) is used, often in epidemiological studies, to perform non-invasive, in vivo measurements of lead in bone. We conducted the first interlaboratory study of XRF via the circulation of nine goat tibiæ in which the mean lead value ranged from 4.0 µg g−1 to 55.3 µg g−1 bone mineral. The test tibiæ were subsequently analyzed via nitric acid digestion followed by lead determination by inductively coupled plasma mass spectrometry (ICP-MS) – along with certified reference materials for bone lead – thus providing measurement traceability to SI units. Analysis of dried bone for lead via nitric acid digestion and ICP-MS yields mass fraction data in units of µg g−1 dry weight. The mean bone lead value based on ICP-MS analysis ranged from 1.8 µg g−1 to 35.8 µg g−1 dry weight. For comparison purposes, XRF-measured Pb values (µg g−1 bone mineral) were converted into the ICP-MS-measured units (µg g−1dry weight bone) by multiplying the former by the average ash fraction from the nine tibiæ. Eight of the XRF systems did not yield a significant bias for any of the nine tibiæ; one system was biased for one of the tibiæ; two systems were biased for two tibiæ; one system was biased for four tibiæ; two systems (813-1 and 804-2) were biased for five tibiæ and one system (801-1) was biased for six of the nine tibiæ. Average bias for the systems (under those particular operating conditions) that were biased for the majority of samples ranged from −2.6 µg g−1 (−15.7%) to 5.1 µg g−1 (30.7%) dry weight bone. All participants now have the ICP-MS data, allowing any corrective actions deemed necessary to be implemented. The ICP-MS data, however, indicated that the lead mass fraction varied considerably with the sampling location within the tibiæ, to the extent of exceeding XRF variability for the higher lead values. Material heterogeneity is an unavoidable reality of

  8. Study of the chemical composition of particulate matter from the Rio de Janeiro metropolitan region, Brazil, by inductively coupled plasma-mass spectrometry and optical emission spectrometry

    NASA Astrophysics Data System (ADS)

    Mateus, Vinícius Lionel; Monteiro, Isabela Luizi Gonçalves; Rocha, Rafael Christian Chávez; Saint'Pierre, Tatiana Dillenburg; Gioda, Adriana

    2013-08-01

    Air quality in the metropolitan region of Rio de Janeiro was evaluated by analysis of particulate matter (PM) in industrial (Santa Cruz) and rural (Seropédica) areas. Total suspended particles (TSP) and fine particulate matter (PM2.5) collected in filters over 24 h were quantified and their chemical composition determined. TSP exceeded Brazilian guidelines (80 μg m- 3) in Santa Cruz, while PM2.5 levels exceeded the World Health Organization guidelines (10 μg m- 3) in both locations. Filters were extracted with water and/or HNO3, and the concentrations of 20 elements, mostly metals, were determined by inductively coupled plasma mass spectrometry (ICP-MS) and optical emission spectrometry (ICP OES). Water soluble inorganic anions were determined by ion chromatography (IC). To estimate the proportion of these elements extracted, a certified reference material (NIST SRM 1648a, Urban Dust) was subjected to the same extraction process. Concordant results were obtained by ICP-MS and ICP OES for most elements. Some elements could not be quantified by both techniques; the most appropriate technique was chosen in each case. The urban dust was also analyzed by the United States Environmental Protection Agency (US EPA) method, which employs a combination of hydrochloric and nitric acids for the extraction, but higher extraction efficiency was obtained when only nitric acid was employed. The US EPA method gave better results only for Sb. In the PM samples, the elements found in the highest average concentrations by ICP were Zn and Al (3-6 μg m- 3). The anions found in the highest average concentrations were SO42 - in PM2.5 (2-4 μg m- 3) and Cl- in TSP (2-6 μg m- 3). Principal component analysis (PCA) in combination with enrichment factors (EF) indicated industrial sources in PM2.5. Analysis of TSP suggested both anthropogenic and natural sources. In conclusion, this work contributes data on air quality, as well as a method for the analysis of PM samples by ICP-MS.

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

    PubMed

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

    2012-03-01

    During criminal investigations involving firearms, the detection of gunshot residues (GSRs) is one of the most important evidences. In the present study, a new method to identify trace evidences of GSRs, deposited around the bullet entrance hole, in different types of fabrics used as targets, is described. The experiments were carried out using a 0.38-inch caliber revolver, and 9-mm and 0.40-inch caliber pistols. Testimonies of 2.25 cm(2) of the fabrics were cut around the bullet entrance and digested with 10% nitric acid. Antimony, barium, and lead were analyzed in the remaining solution using a sector field inductively coupled plasma mass spectrometer. The concentrations of the elements were detected at levels up to few microgram per square centimeter. The use of ternary graphics allowed us to identify specific patterns of distribution for blank samples and the clear distinction between the revolver and pistols used. © 2011 American Academy of Forensic Sciences.

  10. Determination of selenium species in human urine by high performance liquid chromatography and inductively coupled plasma mass spectrometry.

    PubMed

    Quijano, M A; Gutiérrez, A M; Pérez-Conde, M C; Cámara, C

    1999-08-23

    A method developed to determine organic and inorganic selenium species in human urine samples is presented in detail. After a simple sample treatment based on elimination of non-charged organic compounds, selenium species were separated by high performance liquid chromatography (HPLC) on a Spherisorb 5 ODS/AMINO column using two different chromatographic conditions: phosphate buffers at pH 2.8 and 6.0. Detection was carried out using an on-line inductively coupled plasma mass spectrometer (ICP-MS). Trimethylselenonium ion and two unknown selenium species in urine samples were found. Selenium species were shown to have stability problems, with the maximum allowed storage time of 1 week.

  11. Determination of rare earth elements in fluid inclusions by inductively coupled plasma-mass spectrometry (ICP-MS)

    SciTech Connect

    Ghazi, A.M.; Vanko, D.A. ); Roedder, E. ); Seeley, R.C. )

    1993-09-01

    An inductively coupled plasma-mass spectrometer (ICP-MS) is used to determine rare earth element (REE) abundances in fluid inclusions. Quartz concentrates from the Bingham porphyry Cu-Mo deposit, Utah, US, and from a quartz vein in brecciated amphibolite dredged from the Mathematician Ridge, an abandoned spreading center in the eastern Pacific, were prepared by a modified crush-leach method. Leachates and solutions from acid digestion of quartz residue from leaching were analyzed by ICP-MS, using conventional sample introduction. The results demonstrate that the crush-leach method, followed by ICP-MS analysis of leachates, is effective for REE determination. Chondrite-normalized REE patterns for the Bingham samples are light rare earth elements (LREE) enriched, with a small negative Eu anomaly, and the pattern for the Mathematician Ridge sample is nearly flat, with a positive Eu anomaly.

  12. A radiotracer study on the volatilization and transport effects of thermochemical reagents used in the analysis of alumina powders by slurry electrothermal vaporization inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Peschel, Birgit U.; Herdering, Wilhelm; Broekaert, José A. C.

    2007-02-01

    A neutron-activated Al 2O 3 powder SRM 699 (NIST) containing the γ-radiation emitting radionuclides 51Cr, 59Fe, 60Co and 65Zn has been used to study the influence of thermochemical reagents on the volatilization and transport efficiency for these trace elements in electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) of Al 2O 3 powders. From the signals in the γ-spectra for the radiotracers it has been found that less than 2% of the elements Cr, Fe, Co and Zn is left back in a graphite furnace from Al 2O 3 powders at 2200 °C even without addition of a thermochemical reagent and the latter even was found to decrease the volatilization efficiencies. The recovery for the radiotracers on filters at the end of the transport tube as measured from the signals in the γ-spectra, however, was found to increase in most cases (i.e. from about 10% to more than 20%) when Pd(NO 3) 2, Pd(NO 3) 2 + Mg(NO 3) 2, PdCl 2, IrCl 3, SnCl 2, AgCl, NaF, NH 4Cl and NH 4F were added at amounts generally used in electrothermal vaporization inductively coupled plasma mass spectrometry. However, when adding higher amounts as stoichiometrically required for a complete halogenation of the sample matrix in the case of AgCl, C 8F 15O 2Na, IrCl 3 or PdCl 2 the transport efficiencies considerably decrease again. As shown in the case of NH 4Cl the amount of thermochemical reagent used has to be optimized so as to obtain maximum analyte transport efficiencies. A comparison of the influence of NH 4Cl on the transport efficiencies with its influence on the ETV-ICP-MS signals for Fe demonstrates the importance of transport efficiency changes for the effects of thermochemical reagents in electrothermal vaporization inductively coupled plasma mass spectrometry.

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

    PubMed

    Stanislawska, Magdalena; Janasik, Beata; Wasowicz, Wojciech

    2013-12-15

    The toxicity and bioavailability of chromium species are highly dependable on the form or species, therefore determination of total chromium is insufficient for a complete toxicological evaluation and risk assessment. An analytical method for determination of soluble and insoluble Cr (III) and Cr (VI) compounds in welding fume at workplace air has been developed. The total chromium (Cr) was determined by using quadruple inductively coupled plasma mass spectrometry (ICP-MS) equipped with a dynamic reaction cell (DRC(®)). Soluble trivalent and hexavalent chromium compounds were determined by high performance liquid chromatography with inductively coupled plasma mass spectrometry (HPLC-ICP-MS). A high-speed, reversed-phase CR C8 column (PerkinElmer, Inc., Shelton, CT, USA) was used for the speciation of soluble Cr (III) and soluble Cr (VI). The separation was accomplished by interaction of the chromium species with the different components of the mobile phase. Cr (III) formed a complex with EDTA, i.e. retained on the column, while Cr (VI) existed in the solutions as dichromate. Alkaline extraction (2% KOH and 3% Na2CO3) and anion exchange column (PRP-X100, PEEK, Hamilton) were used for the separation of the total Cr (VI). The results of the determination of Cr (VI) were confirmed by the analysis of the certified reference material BCR CRM 545 (Cr (VI) in welding dust). The results obtained for the certified material (40.2±0.6 g kg(-1)) and the values recorded in the examined samples (40.7±0.6 g kg(-1)) were highly consistent. This analytical method was applied for the determination of chromium in the samples in the workplace air collected onto glass (Whatman, Ø 37 mm) and membrane filters (Sartorius, 0.8 μm, Ø 37 mm). High performance liquid chromatography with inductively coupled plasma mass spectrometry is a remarkably powerful and versatile technique for determination of chromium species in welding fume at workplace air. Crown Copyright © 2013 Published by

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

    PubMed

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

    2016-06-22

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

  15. 2D elemental mapping of sections of human kidney stones using laser ablation inductively-coupled plasma-mass spectrometry: Possibilities and limitations

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

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

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

    SciTech Connect

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

    1993-01-01

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

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

    PubMed

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

    2012-10-01

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

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

    SciTech Connect

    Witte, Travis

    2011-01-01

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

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

    PubMed

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

    2012-08-15

    For the identification of human exposure to one of the most toxic compounds, which is methyl mercury (MeHg(+)), fingernail clippings were selected as the matrix of interest. Within this pilot study, six samples from different origins and from people with different food consumption patterns were chosen. Species-analysis of MeHg(+) was performed according to the following procedure: dissolution of the sample material in tetramethylammonium hydroxide (TMAH), derivatisation of MeHg(+) with sodium tetraethylborate (NaBEt(4)), extraction into iso-octane and measurement with gas chromatography hyphenated to inductively coupled plasma mass spectrometry (GC-ICPMS) for the quantification MeHg(+). Copyright © 2012 Elsevier B.V. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

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

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

    PubMed

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

    2015-10-01

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

  2. Characterization, chemometric evaluation, and human health-related aspects of essential and toxic elements in Italian honey samples by inductively coupled plasma mass spectrometry.

    PubMed

    Quinto, Maurizio; Miedico, Oto; Spadaccino, Giuseppina; Paglia, Giuseppe; Mangiacotti, Michele; Li, Donghao; Centonze, Diego; Chiaravalle, A Eugenio

    2016-12-01

    Concentration values of 24 elements (Al, As, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Ge, Hg, Mn, Mo, Pb, Sb, Se, Sn, Sr, Ti, Tl, U, V, and Zn) were determined in 72 honey samples produced in Italy by inductively coupled plasma mass spectrometry (ICP-MS). Considering the recommended established heavy metal daily intakes for humans, in this perspective, an equilibrated and ordinary honey consumption should not be considered matter of concerns for human health, even if particular attention should be addressed if honey is consumed by children, due to different maximum daily heavy metal intakes. Chemometric analysis of the results obtained highlights heavy metal content differences in honey samples obtained from notoriously polluted zones, confirming then that honey can be considered a bio-indicator of environmental pollution. Finally, Pearson coefficients highlighted correlations among element contents in honey samples.

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

    NASA Astrophysics Data System (ADS)

    Kaise, Toshikazu

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

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

  5. Determination of picomolar levels of platinum in estuarine waters: a comparison of cathodic stripping voltammetry and isotope dilution-inductively coupled plasma mass spectrometry.

    PubMed

    Obata, Hajime; Yoshida, Tetsuaki; Ogawa, Hiroshi

    2006-10-27

    A comparative study to determine picomolar concentrations of platinum in natural waters was performed using two different analytical techniques. Results obtained by cathodic stripping voltammetry (CSV) were compared with those obtained by isotope dilution-inductively coupled plasma mass spectrometry (ID-ICPMS) combined with anion exchange resin column extraction method. Using successive UV irradiations with low-pressure mercury (L-Hg) lamp for 4h prior to CSV analysis, the results of both methods were comparable. Without adequate photolytic decomposition, the results obtained using CSV were generally lower than those obtained using ID-ICPMS in the estuarine waters around Tokyo Bay. This difference implies the presence of organically complexed Pt species in the estuarine waters. The Pt enrichment in the middle of the Tokyo Bay estuaries probably reflects the anthropogenic release of Pt from highly populated areas in Tokyo.

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

    SciTech Connect

    Havrilla, George Joseph; Gonzalez, Jhanis

    2015-06-10

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

  7. Laser ablation inductively coupled plasma mass spectrometry for direct analysis of the spatial distribution of trace elements in metallurgical-grade silicon.

    PubMed

    Pisonero, Jorge; Kroslakova, Ivana; Günther, Detlef; Latkoczy, Christopher

    2006-09-01

    The spatial distribution and concentration of impurities in metallurgical-grade silicon (MG-Si) samples (97-99% w/w Si) were investigated by use of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The spatial resolution (120 mum) and low limits of detection (mg kg(-1)) for quality assurance of such materials were studied in detail. The volume-dependent precision and accuracy of non-matrix-matched calibration for quantification of minor elements, using NIST SRM 610 (silicate standard), indicates that LA-ICP-MS is well suited to rapid process control of such materials. Quantitative results from LA-ICP-MS were compared with previously reported literature data obtained by use of ICP-OES and rf-GD-OES. In particular, the distribution of element impurities and their relationship to their different segregation coefficients in silicon is demonstrated.

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

    SciTech Connect

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

    2015-03-01

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

  9. A rapid monitoring method for inorganic arsenic in rice flour using reversed phase-high performance liquid chromatography-inductively coupled plasma mass spectrometry.

    PubMed

    Narukawa, Tomohiro; Chiba, Koichi; Sinaviwat, Savarin; Feldmann, Jörg

    2017-01-06

    A new rapid monitoring method by means of high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) following the heat-assisted extraction was developed for measurement of total inorganic arsenic species in rice flour. As(III) and As(V) eluted at the same retention time and completely separated from organoarsenic species by an isocratic elution program on a reversed phase column. Therefore, neither ambiguous oxidation of arsenite to arsenate nor the integration of two peaks were necessary to determine directly the target analyte inorganic arsenic. Rapid injection allowed measuring 3 replicates within 6min and this combined with a quantitative extraction of all arsenic species from rice flour by a 15min HNO3-H2O2 extraction makes this the fastest laboratory based method for inorganic arsenic in rice flour. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. 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

  11. 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.

  12. Detection of Selenoproteins by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP MS) in Immobilized pH Gradient (IPG) Strips.

    PubMed

    Sonet, Jordan; Mounicou, Sandra; Chavatte, Laurent

    2018-01-01

    In contrast to other trace elements that are cofactors of enzymes and removed from proteins under denaturing conditions, Se is covalently bound to proteins when incorporated into selenoproteins, since it is a component of selenocysteine aminoacid. It implies that selenoproteins can undergo several biochemical separation methods in stringent and chaotropic conditions and still maintain the presence of selenium in the primary sequence. This feature has been used to develop a method for the detection of trace levels of human selenoproteins in cell extracts without the use of radioactive isotopes. The selenoproteins are separated as a function of their isoelectric point (pI) using iso-electrofocusing (IEF) electrophoretic strips and detected by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP MS). This method, therefore referred to as IEF-LA-ICP MS, allowed the detection of several selenoproteins in human cell lines, including Gpx1, Gpx4, TXNRD1, TXNRD2, and SELENOF.

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

    NASA Astrophysics Data System (ADS)

    Ming, Yin; Bing, Li

    1998-09-01

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

  14. Validation and application of a method for the determination of total chromium in rat tissues by inductively coupled plasma mass spectrometry.

    PubMed

    Levine, Keith E; Stout, Matthew D; Ross, Glenn T; Essader, Amal S; Weber, Frank X; Grohse, Peter M; Fernando, Reshan A; Milstein, Lisa S; Hooth, Michelle J; Collins, Bradley J

    2010-04-01

    The validation of a method for the determination of chromium (Cr) in F-344/N rat tissues by inductively coupled plasma-mass spectrometry is described. Samples were analyzed after a rapid, open-vessel microwave digestion procedure. Performance of the method was evaluated using kidney tissue across a concentration range of 0.50-5.00 microg Cr/g tissue. Data for method linearity, accuracy, precision, digest stability, and storage stability are presented along with limits of detection and quantitation data. Data from a method cross-validation for B6C3F1 mouse kidney tissue are also presented. After validation, the method was applied to analyze samples collected in support of two chronic toxicity and carcinogenesis studies conducted by the National Toxicology Program.

  15. Portable laser ablation sampling device for elemental fingerprinting of objects outside the laboratory with laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Glaus, Reto; Koch, Joachim; Günther, Detlef

    2012-06-19

    Laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) is a powerful method for elemental fingerprinting of solid samples in a quasi-nondestructive manner. In order to extend the field of application to objects outside the laboratory, a portable laser ablation sampling device was assembled using a diode pumped solid state laser and fiber-optics. The ablated materials were sampled on membrane filters and subsequently quantified by means of LA-ICPMS. The analytical performance of this approach was investigated for glass and gold reference materials. Accuracies of better than 20% were reached for most elements and typical limits of detection were found to be in the range of 0.01-1 μg/g. In summary, this approach combines spatially resolved sampling with the detection power of ICPMS and enables elemental fingerprinting of objects which cannot be transferred to the laboratory, e.g., archeological artifacts in museums.

  16. Bracketing method with certified reference materials for high precision and accuracy determination of trace cadmium in drinking water by Inductively Coupled Plasma - Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Ketrin, Rosi; Handayani, Eka Mardika; Komalasari, Isna

    2017-01-01

    Two significant parameters to evaluate the measurement results are known as precision and accuracy. Both are associated with indeterminate and determinate error, respectively, that normally happen in such spectrometric measurement method as Inductively Coupled Plasma - Mass Spectrometry (ICP-MS). These errors must be eliminated or suppressed to get high precision and accuracy of the method. Decreasing the errors thus increasing the precision and accuracy of the method. In this study, bracketing method using two-point standard calibration was proposed in order to suppress the indeterminate error caused by instrumental drift thus increasing the result precision, and applied for measuring cadmium in drinking water samples. Certified reference material of ERM CA011b-Hard drinking water UK-metals was used to know the determinate error or measurement bias. When bias is obtained, some corrections are needed to get the accurate measurement result. The result was compared to that by external calibration method.

  17. Determination of platinum group elements by inductively coupled plasma-mass spectrometry combined with nickel sulfide fire assay and tellurium coprecipitation

    NASA Astrophysics Data System (ADS)

    Sun, Yali; Guan, Xiyun; Du, Andao

    1998-09-01

    A method was developed for the determination of trace platinum group elements (PGEs) by nickel sulfide fire assay inductively coupled plasma-mass spectrometry (ICP-MS). With isotope dilution, the improved technique gives precise Os content data. Through the purification of the reagent nickel oxide, reagent blank was greatly reduced. Results obtained for the standard reference materials (SRM) GPt-1-GPt-7(GBW 07288-07294, China), DZ Σ-2 (GBW 07102, China) and Guilin Cu-Ni Ore are in good agreement with the recommended values for platinum group elements. The detection limits ranged from 0.01 to 0.39 ng/g. The relative standard deviations for Ru, Rh, Pd and Ir were less than 5%, for Os less than 1%, and Pt less than 8% for SRM GPt-6.

  18. Determination of Trace Elements in Sintered and Single-Crystal Silicon Carbide by Laser Ablation in Liquid Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Machida, Ryo; Nishioka, Rina; Fujiwara, Masahide; Furuta, Naoki

    2017-01-01

    Laser ablation in liquid (LAL) sampling method transformed hard-to-digest materials to soluble particles, and thus allowed for smooth decomposition by acid digestion. LAL sampling is useful to generate nanoparticles from samples with less contamination. After acid digestion, trace elements in the LAL-sampled particles were analyzed by solution nebulization inductively coupled plasma mass spectrometry (ICPMS). For the first time we demonstrated that LAL-ICPMS can be used to determine trace elements in hard-to-digest samples; sintered SiC and single-crystal SiC. Results obtained by laser ablation ICPMS and LAL-ICPMS were compared in terms of accuracy and detection limits. The detection limits of LAL-ICPMS were 0.04 - 0.4 μg g(-1) for Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Sr, Y, Zr, and W. LAL-ICPMS is expected to be used to control contamination in the manufacturing of semiconductor devices.

  19. Estimates of mineral intakes using food composition tables vs measures by inductively-coupled plasma mass spectrometry: Part 2: sodium, potassium, magnesium, copper, zinc.

    PubMed

    Shimbo, S; Zhang, Z W; Miyake, K; Watanabe, T; Nakatsuka, H; Matsuda-Inoguchi, N; Moon, C S; Higashikawa, K; Ikeda, M

    1999-03-01

    To examine the accuracy of food composition table (FCT)-based estimation of dietary nutrient element intake in reference to the instrumental measurement by inductively-coupled plasma mass spectrometry (ICP-MS), as an extension of the first part of this study. Cross-sectional study. Communities. 782 adult non-smoking women in 21 sites in 4 areas [China (Mainland), Japan, Korea and Malaysia] in Asia. 24-h food duplicate samples offered by the women were subjected 1. to the estimation (E) of daily element intake taking advantage of national food composition tables (FCTs) and 2. to the measurement (M) by inductively-coupled plasma mass spectrometry (ICP-MS). The two sets of the results were compared in terms of the (E)/(M) ratio. Because of the limited availability of the element database in the FCTs, the comparison on Na and K was possible in the 4 areas, whereas that of Mg, Cu and Zn was only in two areas of China (Mainland) and Japan. The (E)/(M) ratio was in a relatively narrow range of 75 to 114% in case of Na, and 91 to 120% for K (with one exception of 201% for K in Malaysia). Correlation coefficients between (E) and (M) were statistically significant for both Na and K in the 4 areas. In cases of Mg, Cu and Zn, agreements were generally poor, and the (E)/(M) ratio was close to 100% only in the cases of Cu and Zn in Japan. In overall evaluation combining the results on Ca, P and Fe in the preceding report with the results in the present report on Na, K, Mg, Cu and Zn, FCT-based estimation generally did not agree with the measure by ICP-MS. The disagreement did not allow precise FCTs-based estimation of dietary intakes of these nutrient elements, possibly except for Na.

  20. Comparison of tunable bandpass reaction cell inductively coupled plasma mass spectrometry with conventional inductively coupled plasma mass spectrometry for the determination of heavy metals in whole blood and urine

    NASA Astrophysics Data System (ADS)

    Nixon, David E.; Neubauer, Kenneth R.; Eckdahl, Steven J.; Butz, John A.; Burritt, Mary F.

    2004-09-01

    A Dynamic Reaction Cell™ inductively coupled plasma mass spectrometer (DRC-ICP-MS) was evaluated for the determination of arsenic, lead, cadmium, mercury, and thallium in urine and whole blood. Reaction cell conditions were evaluated for suppression of ArCl + and CaCl + polyatomic interferences. The reaction gas was 5% hydrogen in argon. Lead, cadmium, mercury, and thallium were determined with the reaction cell vented. Mixture of 2.5% t-butanol, 0.5% HCl, and 2 mg Au/l plus Ga, Rh, and Bi internal standards was used to dilute whole blood and urine. Calibration was achieved using aqueous acidic standards spiked into urine matrix. Urine and whole blood addition calibration curves were nearly identical for all five elements. DRC-ICP-MS detection limits were equivalent or better than conventional ICP-MS. Within run coefficients of variation (CV's) were nearly the same for DRC-ICP-MS and conventional ICP-MS for National Institute of Standards and Technology (NIST) SRM 2670 and BioRad Lyphochek Urine Metals Control. DRC-ICP-MS within run CV's for As, Pb, Cd, and Hg were 1.9%, 4%, 1.7%, and 1.7%, respectively, for NIST 2670 and 2.9%, 1.8%, 3.4%, 1.7%, and 1.0% for BioRad urine. BioRad Lyphochek Whole Blood control concentrations and CV's were: 78 μg/l (3.8%), 284 μg/l (0.52%), and 544 μg/l (0.9%). With the exception of mercury day-to-day CV's for certified whole blood and urine controls were less than 4% on both the DRC-ICP-MS and conventional ICP-MS.

  1. Method validation for determination of cadmium and lead in offal by means of quadrupole inductively coupled plasma mass spectrometry.

    PubMed

    D'Ilio, Sonia; Petrucci, Francesco; D'Amato, Marilena; Di Gregorio, Marco; Senofonte, Oreste; Violante, Nicola

    2008-12-24

    Offal includes viscera and internal organs that have been removed from butchered animals, that may be either directly eaten or processed for the production of other foodstuff. Such organs are able to accumulate high concentrations of potentially toxic heavy metals posing a risk for human health when ingested. Because high levels of Cd and Pb may produce damages to humans, Commission Regulation no. 1881/2006 and its amendment established maximum levels for those two elements in edible bovine, porcine, and ovine offal. In the present study, a method based on microwave acid-assisted digestion and quadrupole inductively coupled plasma mass spectrometric quantification of Cd and Pb in offal was validated according to the EU common standards. The main parameters evaluated in the validation process were: the detection and the quantification limits (LoD, LoQ), the recovery, the repeatability, the within-laboratory reproducibility, the linearity range, and the standard measurement uncertainty. The results obtained for LoD and LoQ in microg kg(-1) were, respectively, Cd, 1.8 and 5.4; Pb, 5.1 and 15.5; meanwhile, the mean recovery was about 98% for Cd and 103% for Pb. Repeatability was around 5% for Cd and 4% for Pb. The expanded standard measurement uncertainty, expressed as percentage and with a coverage factor of 2, was estimated as follows: Cd, 4.9%; Pb, 8.7%. For both elements, the main contribution was due to the within-laboratory reproducibility of the measurements.

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

    PubMed

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

    2012-01-10

    The present study aimed determines lead (Pb), antimony (Sb) and barium (Ba) as the major elements present in GSR in the environmental air of the Ballistics Laboratory of the São Paulo Criminalistics Institute (I.C.-S.P.), São Paulo, SP, Brazil. Micro environmental monitors (mini samplers) were located at selected places. The PM(2.5) fraction of this airborne was collected in, previously weighted filters, and analyzed by sector field inductively coupled plasma mass spectrometer (SF-HR-ICP-MS). The higher values of the airborne lead, antimony and barium, were found at the firing range (lead (Pb): 58.9 μg/m(3); barium (Ba): 6.9 μg/m(3); antimony (Sb): 7.3 μg/m(3)). The mean value of the airborne in this room during 6 monitored days was Pb: 23.1 μg/m(3); Ba: 2.2 μg/m(3); Sb: 1.5 μg/m(3). In the water tank room, the air did not show levels above the limits of concern. In general the airborne lead changed from day to day, but the barium and antimony remained constant. Despite of that, the obtained values suggest that the workers may be exposed to airborne lead concentration that can result in an unhealthy environment and could increase the risk of chronic intoxication. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

  3. Determination of selenium and tellurium compounds in biological samples by ion chromatography dynamic reaction cell inductively coupled plasma mass spectrometry.

    PubMed

    Kuo, Chia-Yi; Jiang, Shiuh-Jen

    2008-02-15

    An ion chromatography-inductively coupled plasma mass spectrometric (IC-ICP-MS) method for the speciation of selenium and tellurium compounds namely selenite [Se(IV)], selenate [Se(VI)], Se-methylselenocysteine (MeSeCys), selenomethione (SeMet), tellurite [Te(IV)] and tellurate [Te(VI)] is described. Chromatographic separation is performed in gradient elution mode using 0.5 mmol L(-1) ammonium citrate in 2% methanol (pH 3.7) and 20 mmol L(-1) ammonium citrate in 2% methanol (pH 8.0). The analyses are carried out using dynamic reaction cell (DRC) ICP-MS. The DRC conditions have also been optimized to obtain interference free measurements of (78)Se(+) and (80)Se(+) which are otherwise interfered by (38)Ar(40)Ar(+) and (40)Ar(40)Ar(+), respectively. The detection limits of the procedure are in the range 0.01-0.03 ng Se mL(-1) and 0.01-0.08 ng Te mL(-1), respectively. The accuracy of the method has been verified by comparing the sum of the concentrations of individual species obtained by the present procedure with the total concentration of the elements in two NIST SRMs Whole Milk Powder RM 8435 and Rice Flour SRM 1568a. The selenium and tellurium species are extracted from milk powder and rice flour samples by using Protease XIV at 70 degrees C on a water bath for 30 min.

  4. The separation of arsenic metabolites in urine by high performance liquid chromatographyinductively coupled plasma-mass spectrometry

    PubMed Central

    Chung, Jin-Yong; Lim, Hyoun-Ju; Kim, Young-Jin; Song, Ki-Hoon; Kim, Byoung-Gwon; Hong, Young-Seoub

    2014-01-01

    Objectives The purpose of this study was to determine a separation method for each arsenic metabolite in urine by using a high performance liquid chromatography (HPLC)- inductively coupled plasma-mass spectrometer (ICP-MS). Methods Separation of the arsenic metabolites was conducted in urine by using a polymeric anion-exchange (Hamilton PRP X-100, 4.6 mm×150 mm, 5 μm) column on Agilent Technologies 1260 Infinity LC system coupled to Agilent Technologies 7700 series ICP/MS equipment using argon as the plasma gas. Results All five important arsenic metabolites in urine were separated within 16 minutes in the order of arsenobetaine, arsenite, dimethylarsinate, monomethylarsonate and arsenate with detection limits ranging from 0.15 to 0.27 μg/L (40 μL injection). We used GEQUAS No. 52, the German external quality assessment scheme and standard reference material 2669, National Institute of Standard and Technology, to validate our analyses. Conclusions The method for separation of arsenic metabolites in urine was established by using HPLC-ICP-MS. This method contributes to the evaluation of arsenic exposure, health effect assessment and other bio-monitoring studies for arsenic exposure in South Korea. PMID:25384385

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

    NASA Astrophysics Data System (ADS)

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

    2000-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-05-01

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

  7. Determination of depleted uranium in fish: validation of a confirmatory method by dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS).

    PubMed

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

    2007-08-06

    Depleted uranium (DU) is a by-product of the uranium enrichment process for nuclear fuel. According to the Commission Decision 2002/657/EC, a confirmatory method for the quantification of DU in freeze-dried fish was developed by isotope ratio dynamic reaction cell inductively coupled plasma-mass spectrometry (IR-DRC-ICP-MS). A preliminary study was performed to determine the following parameters: instrumental detection limit (IDL), isotopic ratio measurement limit (IRML), percentage of DU (P(DU)) in presence of natural uranium (NU) and limit of quantification (LoQ(DU)). The analyses were carried out by means of IR-DRC-ICP-MS. Ammonia was the reaction gas used for the dynamic reaction cell. In addition, a sector field inductively coupled plasma mass spectrometer (SF-ICP-MS) was employed to calculate the within-laboratory reproducibility. For the confirmatory method the following parameters were determined: (a) trueness; (b) precision; (c) critical concentrations alpha and beta (CC(alpha), CC(beta)); (d) specificity; (e) stability. Trueness was assessed by using the recovery tests. The recovery and within-laboratory reproducibility were determined by fortifying the blank digested solution of dogfish tissue: six aliquots were fortified at 1, 1.5 and 2 times the LOQ(DU) with 25.0, 37.5 and 50.0 ng L(-1) or 4.16, 6.24, 8.32 microg kg(-1) with a recovery of -8.2, +9.5 and +9.6%, respectively and a within-laboratory reproducibility (three analytical run) of 15.5, 8.0 and 11.0%, respectively. The results for the decision limit and the detection capability were: CC(alpha) = 11.69 ng L(-1) and CC(beta) = 19.8 ng L(-1). The digested solutions resulted to be stable during testing time (60 days) and the method can be considered highly specific as well.

  8. Non-linear signal response functions and their effects on the statistical and noise cancellation properties of isotope ratio measurements by multi-collector plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Doherty, W.

    2013-07-01

    A nebulizer-centric response function model of the analytical inductively coupled argon plasma ion source was used to investigate the statistical frequency distributions and noise reduction factors of simultaneously measured flicker noise limited isotope ion signals and their ratios. The response function model was extended by assuming i) a single gaussian distributed random noise source (nebulizer gas pressure fluctuations) and ii) the isotope ion signal response is a parabolic function of the nebulizer gas pressure. Model calculations of ion signal and signal ratio histograms were obtained by applying the statistical method of translation to the non-linear response function model of the plasma. Histograms of Ni, Cu, Pr, Tl and Pb isotope ion signals measured using a multi-collector plasma mass spectrometer were, without exception, negative skew. Histograms of the corresponding isotope ratios of Ni, Cu, Tl and Pb were either positive or negative skew. There was a complete agreement between the measured and model calculated histogram skew properties. The nebulizer-centric response function model was also used to investigate the effect of non-linear response functions on the effectiveness of noise cancellation by signal division. An alternative noise correction procedure suitable for parabolic signal response functions was derived and applied to measurements of isotope ratios of Cu, Ni, Pb and Tl. The largest noise reduction factors were always obtained when the non-linearity of the response functions was taken into account by the isotope ratio calculation. Possible applications of the nebulizer-centric response function model to other types of analytical instrumentation, large amplitude signal noise sources (e.g., lasers, pumped nebulizers) and analytical error in isotope ratio measurements by multi-collector plasma mass spectrometry are discussed.

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

    PubMed

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

    2016-06-21

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

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

    SciTech Connect

    Allen, Lloyd A.

    1996-10-17

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

  11. Evaluation of pyrolysis curves for volatile elements in aqueous standards and carbon-containing matrices in electrothermal vaporization inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Silva, A. F.; Welz, B.; de Loos-Vollebregt, M. T. C.

    2008-07-01

    Pyrolysis curves in electrothermal atomic absorption spectrometry (ET AAS) and electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) have been compared for As, Se and Pb in lobster hepatopancreas certified reference material using Pd/Mg as the modifier. The ET AAS pyrolysis curves confirm that the analytes are not lost from the graphite furnace up to a pyrolysis temperature of 800 °C. Nevertheless, a downward slope of the pyrolysis curve was observed for these elements in the biological material using ETV-ICP-MS. This could be related to a gain of sensitivity at low pyrolysis temperatures due to the matrix, which can act as carrier and/or promote changes in the plasma ionization equilibrium. Experiments with the addition of ascorbic acid to the aqueous standards confirmed that the higher intensities obtained in ETV-ICP-MS are related to the presence of organic compounds in the slurry. Pyrolysis curves for As, Se and Pb in coal and coal fly ash were also investigated using the same Pd/Mg modifier. Carbon intensities were measured in all samples using different pyrolysis temperatures. It was observed that pyrolysis curves for the three analytes in all slurry samples were similar to the corresponding graphs that show the carbon intensity for the same slurries for pyrolysis temperatures from 200 °C up to 1000 °C.

  12. Metal imaging in non-denaturating 2D electrophoresis gels by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for the detection of metalloproteins.

    PubMed

    Becker, J Susanne; Lobinski, Ryszard; Becker, J Sabine

    2009-01-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was developed as a powerful analytical technique for metal imaging of 2D gels for the detection of metalloproteins in rat kidney after electrophoretic separation. Protein complexes, extracted with water, were separated in their native state in the first and second dimension by blue native gel electrophoresis (BN-PAGE). Essential and toxic metals, such as zinc, copper, iron, manganese and lead, were monitored by LA-ICP-MS after gel ablation by a focused laser beam in a way that the total surface of a selected fragment of the gel was totally ablated. The metal distribution of this part of the gel was then constructed by plotting the metal (isotope) signal intensity as a function of the x,y (isoelectric point, molecular mass) coordinates of the gel. The proteins at locations rich in metals were cut out, digested with trypsin and analyzed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS).

  13. Metallurgical and chemical characterization of copper alloy reference materials within laser ablation inductively coupled plasma mass spectrometry: Method development for minimally-invasive analysis of ancient bronze objects

    NASA Astrophysics Data System (ADS)

    Walaszek, Damian; Senn, Marianne; Faller, Markus; Philippe, Laetitia; Wagner, Barbara; Bulska, Ewa; Ulrich, Andrea

    2013-01-01

    The chemical composition of ancient metal objects provides important information for manufacturing studies and authenticity verification of ancient copper or bronze artifacts. Non- or minimal-destructive analytical methods are preferred to mitigate visible damage. Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) enables the determination of major elements as well as impurities down to lower ppm-levels, however, accuracy and precision of analysis strongly depend on the homogeneity of reference materials used for calibration. Moreover, appropriate analytical procedures are required e.g. in terms of ablation strategies (scan mode, spot size, etc.). This study reviews available copper alloy (certified) reference materials — (C)RMs from different sources and contributes new metallurgical data on homogeneity and spatial elemental distribution. Investigations of the standards were performed by optical and scanning electron microscopy with X-ray spectrometry (SEM-EDX) for the following copper alloy and bronze (certified) reference materials: NIST 454, BAM 374, BAM 211, BAM 227, BAM 374, BAM 378, BAS 50.01-2, BAS 50.03-4, and BAS 50.04-4. Additionally, the influence of inhomogeneities on different ablation and calibration strategies is evaluated to define an optimum analytical strategy in terms of line scan versus single spot ablation, variation of spot size, selection of the most appropriate RMs or minimum number of calibration reference materials.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  15. Imaging of metals, metalloids, and non-metals by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) in biological tissues.

    PubMed

    Becker, J Sabine; Becker, J Susanne

    2010-01-01

    The determination of the localization and distribution of essential and beneficial metals (e.g., Cu, Fe, Zn, Mn, Co, Ti, Al, Ca, K, Na, Cr and others), toxic metals (like Cd, Pb, Hg, U), metalloids (e.g., As, Se, Sb), and non-metals (such as C, S, P, Cl, I) in biological tissues is a challenging task for life science studies. Over the past few years, the development and application of mass spectrometric imaging (MSI) techniques for elements has been rapidly growing in the life sciences in order to investigate the uptake and the transport of both essential and toxic metals in plant and animal sections. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is a very sensitive and efficient trace, surface, and isotopic analytical technique for biological samples. LA-ICP-MS is increasingly utilized as an elemental mass spectrometric technique using double-focusing sector field (LA-ICP-SFMS) or quadrupole mass spectrometers (LA-ICP-QMS) to produce images of detailed regionally specific element distributions in thin biological tissue sections. Nowadays, MSI studies focus on brain research for studying neurodegenerative diseases such as Alzheimer's or Parkinson's, stroke, or tumor growth, or for the imaging of cancer biomarkers in tissue sections.The combination of the mass spectrometry imaging of metals by LA-ICP-MS with proteomics using biomolecular mass spectrometry (such as MALDI-MS or ESI-MS) to identify metal-containing proteins has become an important strategy in the life sciences. Besides the quantitative imaging of metals, non-metals and metalloids in biological tissues, LA-ICP-MS has been utilized for imaging metal-containing proteins in a 2D gel after electrophoretic separation of proteins. Recent progress in applying LA-ICP-MS in life science studies will be reviewed including the imaging of thin slices of biological tissue and applications in proteome analysis in combination with MALDI/ESI-MS to analyze metal-containing proteins.

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

    SciTech Connect

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

    2010-05-01

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

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

    PubMed

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

    2015-03-03

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

  18. Flow-injection technique for determination of uranium and thorium isotopes in urine by inductively coupled plasma mass spectrometry.

    PubMed

    Benkhedda, Karima; Epov, Vladimir N; Evans, R Douglas

    2005-04-01

    A sensitive and efficient flow-injection (FI) preconcentration and matrix-separation technique coupled to sector field ICP-mass spectrometry (SF-ICP-MS) has been developed and validated for simultaneous determination of ultra-low levels of uranium (U) and thorium (Th) in human urine. The method is based on selective retention of U and Th from a urine matrix, after microwave digestion, on an extraction chromatographic TRU resin, as an alternative to U/TEVA resin, and their subsequent elution with ammonium oxalate. Using a 10 mL sample, the limits of detection achieved for 238U and 232Th were 0.02 and 0.03 ng L(-1), respectively. The accuracy of the method was checked by spike-recovery measurements. Levels of U and Th in human urine were found to be in the ranges 1.86-5.50 and 0.176-2.35 ng L(-1), respectively, well in agreement with levels considered normal for non-occupationally exposed persons. The precision obtained for five replicate measurements of a urine sample was 2 and 3% for U and Th, respectively. The method also enables on-line measurements of the 235U/238U isotope ratios in urine. Precision of 0.82-1.04% (RSD) was obtained for 235U/238U at low ng L(-1) levels, using the FI transient signal approach.

  19. Determination of total and isotopic uranium by inductively coupled plasma-mass spectrometry at the Fernald Environmental Management Project

    SciTech Connect

    Miller, F.L.; Bolin, R.N.; Feller, M.T.; Danahy, R.J.

    1995-04-01

    At the Fernald Environmental Management Project (FEMP) in southwestern Ohio, ICP-mass spectrometry (ICP-MS), with sample introduction by peristaltic pumping, is used to determine total and isotopic uranium (U-234, U-235, U-236 and U-238) in soil samples. These analyses are conducted in support of the environmental cleanup of the FEMP site. Various aspects of the sample preparation and instrumental analysis will be discussed. Initial sample preparation consists of oven drying to determine moisture content, and grinding and rolling to homogenize the sample. This is followed by a nitric/hydrofluoric acid digestion to bring the uranium in the sample into solution. Bismuth is added to the sample prior to digestion to monitor for losses. The total uranium (U-238) content of this solution and the U{sup 235}/U{sup 238} ratio are measured on the first pass through the ICP-MS. To determine the concentration of the less abundant U{sup 234} and U{sup 236} isotopes, the digestate is further concentrated by using Eichrom TRU-Spec extraction columns before the second pass through the ICP-MS. Quality controls for both the sample preparation and instrumental protocols will also be discussed. Finally, an explanation of the calculations used to report the data in either weight percent or activity units will be given.

  20. Optimization of a single-drop microextraction method for multielemental determination by electrothermal vaporization inductively coupled plasma mass spectrometry following in situ vapor generation

    NASA Astrophysics Data System (ADS)

    Gil, Sandra; de Loos-Vollebregt, Margaretha T. C.; Bendicho, Carlos

    2009-03-01

    A headspace single-drop microextraction (HS-SDME) method has been developed in combination with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) for the simultaneous determination of As, Sb, Bi, Pb, Sn and Hg in aqueous solutions. Vapor generation is carried out in a 40 mL volume closed-vial containing a solution with the target analytes in hydrochloric acid and potassium ferricyanide medium. Hydrides (As, Sb, Bi, Pb, Sn) and Hg vapor are trapped onto an aqueous single drop (3 µL volume) containing Pd(II), followed by the subsequent injection in the ETV. Experimental variables such as medium composition, sodium tetrahydroborate (III) volume and concentration, stirring rate, extraction time, sample volume, ascorbic acid concentration and palladium amount in the drop were fully optimized. The limits of detection (LOD) (3 σ criterion) of the proposed method for As, Sb, Bi, Pb, Sn and Hg were 0.2, 0.04, 0.01, 0.07, 0.09 and 0.8 µg/L, respectively. Enrichment factors of 9, 85, 138, 130, 37 and 72 for As, Sb, Bi, Pb, Sn and Hg, respectively, were achieved in 210 s. The relative standard deviations ( N = 5) ranged from 4 to 8%. The proposed HS-SDME-ETV-ICP-MS method has been applied for the determination of As, Sb, Bi, Pb, Sn and Hg in NWRI TM-28.3 certified reference material.

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

    PubMed

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

    2010-05-15

    A tungsten boat furnace vaporization inductively coupled plasma mass spectrometry (TBF/ICP-MS) method has been applied to the direct determination of bromine in plastic samples. In the pretreatment, the plastic sample is spread over a small sample cuvette made of tungsten by treating it with a strongly basic organic solution, e.g., octanol or diisobutyl ketone in the presence of potassium hydroxide. The cuvette is placed on a tungsten boat furnace, with which the electrothermal vaporizer is equipped. At the vaporization step, a widely spread thin layer of the sample facilitates its efficient evaporation and introduction into an ICP mass spectrometer. The most remarkable feature is that all the bromine species in plastic samples are decomposed to form a thermally stable inorganic salt during the pretreatment procedure. Therefore, the bromine content in plastic samples can be measured by a calibration curve method constructed with an aqueous standard solution of potassium bromate(V). The detection limit (3sigma) was estimated to be 0.77 pg of bromine, which corresponds to a concentration of 0.31 ng g(-1) of bromine in plastic samples when a sample amount taken of 2.5 mg is studied. The relative standard deviation was calculated to be 2.2%. Analytical results of some plastic samples, which contained both inorganic bromide salts and also organic bromine species, are given. Copyright (c) 2010 John Wiley & Sons, Ltd.

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

    PubMed Central

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

    2014-01-01

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

  3. Microwave-assisted extraction of rare earth elements from petroleum refining catalysts and ambient fine aerosols prior to inductively coupled plasma-mass spectrometry.

    PubMed

    Kulkarni, Pranav; Chellam, Shankararaman; Mittlefehldt, David W

    2007-01-09

    A robust microwave-assisted acid digestion procedure followed by inductively coupled plasma-mass spectrometry (ICP-MS) was developed to quantify rare earth elements (REEs) in fluidized-bed catalytic cracking (FCC) catalysts and atmospheric fine particulate matter (PM(2.5)). High temperature (200 degrees C), high pressure (200 psig), acid digestion (HNO(3), HF and H(3)BO(3)) with 20 min dwell time effectively solubilized REEs from six fresh catalysts, a spent catalyst and PM(2.5). This method was also employed to measure 27 non-REEs including Na, Mg, Al, Si, K, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Zr, Mo, Cd, Cs, Ba, Pb and U. Complete extraction of several REEs (Y, La, Ce, Pr, Nd, Tb, Dy and Er) required HF indicating that they were closely associated with the aluminosilicate structure of the zeolite FCC catalysts. Internal standardization using (115)In quantitatively corrected non-spectral interferences in the catalyst digestate matrix. Inter-laboratory comparison using ICP-optical emission spectroscopy (ICP-OES) and instrumental neutron activation analysis (INAA) demonstrated the applicability of the newly developed analytical method for accurate analysis of REEs in FCC catalysts. The method developed for FCC catalysts was also successfully implemented to measure trace to ultra-trace concentrations of La, Ce, Pr, Nd, Sm, Gd, Eu and Dy in ambient PM(2.5) in an industrial area of Houston, TX.

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

    PubMed Central

    Philippe, Allan; Schaumann, Gabriele E.

    2014-01-01

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

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

    PubMed

    Philippe, Allan; Schaumann, Gabriele E

    2014-01-01

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

  6. Mercury speciation in thawed out and refrozen fish samples by gas chromatography coupled to inductively coupled plasma mass spectrometry and atomic fluorescence spectroscopy.

    PubMed

    Krystek, Petra; Ritsema, Rob

    2005-01-01

    Different sub-sampling procedures were applied for the determination of mercury species (as total mercury Hg, methylmercury MeHg+ and inorganic mercury Hg2+) in frozen fish meat. Analyses were carried out by two different techniques. After the sample material was pre-treated by microwave digestion, atomic fluorescence spectroscopy (AFS) was used for the determination of total Hg. Speciation analysis was performed according to the following procedure: dissolution of sample material in tetramethylammonium hydroxide (TMAH), derivatisation with sodium tetraethylborate (NaBEt4), extraction into isooctane and measurement with gas chromatography inductively coupled plasma mass spectrometry (GC-ICPMS) for the identification and quantification of methylmercury (MeHg+) and inorganic mercury (Hg2+). The concentration range of total Hg measured in the shark fillets is between 0.9 and 3.6 microg g(-1) thawed out shark fillet. Speciation analysis leads to > or =94% Hg present as MeHg+. Homogeneity, storage conditions and stability of analytical species and sample materials have great influence on analytical results. Sub-sampling of half-frozen/partly thawed out fish and analysis lead to significantly different concentrations, which are on average a factor of two lower.

  7. Quantitative analysis of iron-containing protein myoglobin in different foodstuffs by liquid chromatography coupled to high-resolution inductively coupled plasma mass spectrometry.

    PubMed

    Harrington, Chris F; Elahi, Selvarani; Merson, Sheila A; Ponnampalavanar, Punitha

    2004-01-01

    Quantitative determination was made of the iron-containing protein myoglobin in a range of different foods, including meat, processed meat, fish, and shellfish, by liquid chromatography coupled to a double-focusing sector field inductively coupled plasma mass spectrometry (ICP-MS). The concentration of myoglobin determined in the samples ranged from 0 to 6.5 mg/kg, and the analytical precision (coefficient of variation) for the analysis of 8 replicate raw steak extracts was 2.1%. By using a double-focusing ICP-MS instrument, direct on-line detection of the most abundant iron isotope 56Fe was possible without interference from a major polyatomic interference (40Ar16O). Separation of myoglobin from other iron-containing compounds was facilitated by use of a gel filtration column (TSK Gel G2000SW) and Tris buffer (pH 7.2). The chromatographic column was coupled directly to the nebulizer of the ICP-MS instrument by a short piece of PEEK tubing. To ensure sufficient quality control throughout the study, a raw beefsteak sample was developed as an in-house reference material. The concentration of the heme-iron-containing protein myoglobin in this sample was determined by the developed method and independently by a conventional spectrophotometric method. The agreement between the 2 analytical techniques was very good. The detection limit (3 times the signal/noise ratio for a blank) of the reported method for myoglobin was 0.85 ng Fe/L.

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

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

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

  9. Elemental bioimaging of nanosilver-coated prostheses using X-ray fluorescence spectroscopy and laser ablation-inductively coupled plasma-mass spectrometry.

    PubMed

    Blaske, Franziska; Reifschneider, Olga; Gosheger, Georg; Wehe, Christoph A; Sperling, Michael; Karst, Uwe; Hauschild, Gregor; Höll, Steffen

    2014-01-07

    The distribution of different chemical elements from a nanosilver-coated bone implant was visualized, combining the benefits of two complementary methods for elemental bioimaging, the nondestructive micro X-ray fluorescence (μ-XRF), and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Challenges caused by the physically inhomogeneous materials including bone and soft tissues were addressed by polymer embedding. With the use of μ-XRF, fast sample mapping was achieved obtaining titanium and vanadium signals from the metal implant as well as phosphorus and calcium signals representing hard bone tissue and sulfur distribution representing soft tissues. Only by the use of LA-ICP-MS, the required high sensitivity and low detection limits for the determination of silver were obtained. Metal distribution within the part of cancellous bone was revealed for silver as well as for the implant constituents titanium, vanadium, and aluminum. Furthermore, the detection of coinciding high local zirconium and aluminum signals at the implant surface indicates remaining blasting abrasive from preoperative surface treatment of the nanosilver-coated device.

  10. Determination of arsenic in traditional Chinese medicine by microwave digestion with flow injection-inductively coupled plasma mass spectrometry (FI-ICP-MS).

    PubMed

    Ong, E S; Yong, Y L; Woo, S O

    1999-01-01

    A simple, rapid, and sensitive method with high sample throughput was developed for determining arsenic in traditional Chinese medicine (TCM) in the form of uncoated tablets, sugar-coated tablets, black pills, capsules, powders, and syrups. The method involves microwave digestion with flow injection-inductively coupled plasma mass spectrometry (FI-ICP-MS). Method precision was 2.7-10.1% (relative standard deviation, n = 6) for different concentrations of arsenic in different TCM samples analyzed by different analysts on different days. Method accuracy was checked with a certified reference material (sea lettuce, Ulva lactuca, BCR CRM 279) for external calibration and by spiking arsenic standard into different TCMs. Recoveries of 89-92% were obtained for the certified reference material and higher than 95% for spiked TCMs. Matrix interference was insignificant for samples analyzed by the method of standard addition. Hence, no correction equation was used in the analysis of arsenic in the samples studied. Sample preparation using microwave digestion gave results that were very similar to those obtained by conventional wet acid digestion using nitric acid.

  11. Laser ablation-inductively coupled plasma-mass spectrometry imaging of white and gray matter iron distribution in Alzheimer's disease frontal cortex.

    PubMed

    Hare, Dominic J; Raven, Erika P; Roberts, Blaine R; Bogeski, Mirjana; Portbury, Stuart D; McLean, Catriona A; Masters, Colin L; Connor, James R; Bush, Ashley I; Crouch, Peter J; Doble, Philip A

    2016-08-15

    Iron deposition in the brain is a feature of normal aging, though in several neurodegenerative disorders, including Alzheimer's disease, the rate of iron accumulation is more advanced than in age-matched controls. Using laser ablation-inductively coupled plasma-mass spectrometry imaging we present here a pilot study that quantitatively assessed the iron content of white and gray matter in paraffin-embedded sections from the frontal cortex of Alzheimer's and control subjects. Using the phosphorus image as a confirmed proxy for the white/gray matter boundary, we found that increased intrusion of iron into gray matter occurs in the Alzheimer's brain compared to controls, which may be indicative of either a loss of iron homeostasis in this vulnerable brain region, or provide evidence of increased inflammatory processes as a response to chronic neurodegeneration. We also observed a trend of increasing iron within the white matter of the frontal cortex, potentially indicative of disrupted iron metabolism preceding loss of myelin integrity. Considering the known potential toxicity of excessive iron in the brain, our results provide supporting evidence for the continuous development of novel magnetic resonance imaging approaches for assessing white and gray matter iron accumulation in Alzheimer's disease. Crown Copyright © 2016. Published by Elsevier Inc. All rights reserved.

  12. Determination of trace elements in medicinal activated charcoal using slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry with low vaporization temperature.

    PubMed

    Chen, Chien-Chou; Jiang, Shiuh-Jen; Sahayam, A C

    2015-01-01

    The determination of Cd, Sb, Te, Hg, Tl and Pb in medicinal activated charcoal by ultrasonic slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry (USS-ETV-ICP-MS) was described. EDTA was used as the modifier to enhance the volatility of elements studied. The influences of instrument operating conditions and slurry preparation on the ion signals were studied. A relatively low vaporization temperature of 1000°C was used, which separated the analyte from the major matrix components that improved ion signals. The method has been applied to determine Cd, Sb, Te, Hg, Tl and Pb in an NIST SRM 1633b Coal Fly Ash reference material and three brands of medicinal activated charcoal capsules using isotope dilution and standard addition calibration methods. The concentrations that are in ng g(-1) levels were in good agreement between different calibration methods. The precision between sample replicates was better than 7% with USS-ETV-ICP-MS technique. The method detection limit estimated from standard addition curves was 0.4, 0.3, 0.3, 0.3, 0.04 and 0.9 ng g(-1) for Cd, Sb, Te, Hg, Tl and Pb, respectively, in original medicinal activated charcoal.

  13. Evaluation of microwave and ultrasound extraction procedures for arsenic speciation in bivalve mollusks by liquid chromatography-inductively coupled plasma-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Santos, Clarissa M. M.; Nunes, Matheus A. G.; Barbosa, Isa S.; Santos, Gabriel L.; Peso-Aguiar, Marlene C.; Korn, Maria G. A.; Flores, Erico M. M.; Dressler, Valderi L.

    2013-08-01

    Liquid chromatography-inductively coupled plasma-mass spectrometry (LC-ICP-MS) was used for arsenic speciation analysis in tissues of bivalve mollusks (Anomalocardia brasiliana sp. and Macoma constricta sp.). Microwave and ultrasound radiation, combined with different extraction conditions (solvent, sample amount, time, and temperature), were evaluated for As-species extraction from the mollusks' tissues. Accuracy, extraction efficiency, and the stability of As species were evaluated by analyzing certified reference materials (DORM-2, dogfish muscle; BCR-627, tuna fish tissue; and SRM 1566b, oyster tissue) and analyte recovery tests. The best conditions were found to be microwave-assisted extraction using 200 mg of samples and water at 80 °C for 6 min. The agreement of As-species concentration in samples ranged from 97% to 102%. Arsenobetaine (AsB) was the main species present in bivalve mollusk tissues, while monomethylarsonic acid (MMA) and arsenate (As(V)) were below the limit of quantification (0.001 and 0.003 μg g- 1, respectively). Two unidentified As species also were detected and quantified. The sum of the As-species concentration was in agreement (90 to 104%), with the total As content determined by ICP-MS after sample digestion.

  14. Particle size characterization of titanium dioxide in sunscreen products using sedimentation field-flow fractionation-inductively coupled plasma-mass spectrometry.

    PubMed

    Samontha, Atitaya; Shiowatana, Juwadee; Siripinyanond, Atitaya

    2011-01-01

    Sedimentation field-flow fractionation-inductively coupled plasma-mass spectrometry (SdFFF-ICP-MS) was successfully applied to investigate particle size distribution of titanium dioxide (TiO(2)) in sunscreen samples after hexane extraction to remove organic components from the samples. Three brands of sunscreen products of various sun protection factor (SPF) value were used as samples. Different particle size distribution profiles were observed for sunscreen samples of various brands and SPF values; however, the particle size distributions of titanium dioxide in most sunscreen samples investigated in this work were larger than 100 nm. The titanium dioxide concentrations were higher for the products of higher SPF values. By comparing the results obtained from online SdFFF-ICP-MS and those from the off-line ICP-MS determination of titanium after acid digestion, ICP-MS was found to effectively atomize and ionize the titanium dioxide particle without the need for acid digestion of the samples. Therefore, the online coupling between SdFFF and ICP-MS could be effectively used to provide quantitative information of titanium dioxide concentrations across particle size distribution profiles.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  16. 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.

  17. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

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

    NASA Astrophysics Data System (ADS)

    Smith, F.

    2013-12-01

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

  20. [Analysis of X-ray fluorescence spectroscopy and plasma mass spectrometry of the Guidong granite body and its implications to granite evolution].

    PubMed

    Li, Hong-Wei; Chen, Guo-Neng; Peng, Zhuo-Lun

    2013-07-01

    The Guidong composite granite body (CGB) located in the north Guangdong Province consists of numerous rock bodies formed respectively in the early and late Jurassic and early Cretaceous. Analysis of the granites of different period with X-ray fluorescence spectroscopy and plasma mass spectrometry indicates: (1) From the top of a granite body downwards, the felsic components of rock decrease, while the mafic and sigmaREE, LREE/HREE, (La/Yb)N, as well as delta Eu value increase, suggesting the material differentiation in the in-situ melting of crustal rocks and crystallisation of magma; (2) From old to young of the different period granite-massifs in the Guidong CGB, the felsic compositions totally decrease, and the mafic components, sigmaEE, LREE/HREE, (La/Yb)N, and delta Eu value increase as well, implying multiple crustal melting (remelting) events in the Mesozoic in this area; and (3) Primitive mantle-normalized spider diagram for trace elements of Guidong CGB suggests high maturity of the crust involved in the in-situ melting.

  1. Separation and characterization of metallothionein in the liver of sea turtles by high performance liquid chromatographylinductively coupled plasma-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Shinsuke, T.; Yasumi, A.; Takashi, K.

    2003-05-01

    To investigate whether trace metals bind to metallothioneins (MTs) in the hepatocytosol of green turtles (Chelonia mydas) and hawksbill turtles (Eretmochelys imbricata), MT fraction was obtained by ultracentrifugation and gel filtration methods. MTs separated from hepatocytosol were further purified and characterized by high performance liquid chromatography/inductively coupled plasma-mass spectrometry. In addition, the involvement of MTs in the accumulation of trace metals in the liver of sea turtle was examine. Gel filtration analysis showed that significant amounts of Cu, Zn, Ag and Cd were bound to MT in the cytosol of sea turtles, suggesting that such trace metals were primarily detoxified by interaction with MTs in the liver. Elution profiles of these trace metals by anion-exchange chromatography were different between green turtles and hawksbill turtles. These results suggest the presence of multiple isoforms of MT in the liver of both sea turtles; however, constituents of isoforms were different between green and hawksbill turtles. In both species, we observed the elevation of the height of a specific peak in elution profile with an increase in Cu concentration in hepatocytosol. This result suggests the presence of a novel MT isoform related to copper accumulation in the liver of sea turtles.

  2. Determination of trace sulfur in biodiesel and diesel standard reference materials by isotope dilution sector field inductively coupled plasma mass spectrometry.

    PubMed

    Amais, Renata S; Long, Stephen E; Nóbrega, Joaquim A; Christopher, Steven J

    2014-01-02

    A method is described for quantification of sulfur at low concentrations on the order of mgkg(-1) in biodiesel and diesel fuels using isotope dilution and sector field inductively coupled plasma mass spectrometry (ID-SF-ICP-MS). Closed vessel microwave-assisted digestion was employed using a diluted nitric acid and hydrogen peroxide decomposition medium to reduce sample dilution volumes. Medium resolution mode was employed to eliminate isobaric interferences at (32)S and (34)S related to polyatomic phosphorus and oxygen species, and sulfur hydride species. The method outlined yielded respective limits of detection (LOD) and limits of quantification (LOQ) of 0.7 mg kg(-1) S and 2.5 mg kg(-1) S (in the sample). The LOD was constrained by instrument background counts at (32)S but was sufficient to facilitate value assignment of total S mass fraction in NIST SRM 2723b Sulfur in Diesel Fuel Oil at 9.06±0.13 mg kg(-1). No statistically significant difference at a 95% confidence level was observed between the measured and certified values for certified reference materials NIST SRM 2773 B100 Biodiesel (Animal-Based), CENAM DRM 272b and NIST SRM 2723a Sulfur in Diesel Fuel Oil, validating method accuracy.

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

    PubMed

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

    2015-11-01

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

  4. A comparison of the use of refractive index (RI) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for the provenance establishment of glass bottles.

    PubMed

    May, Christopher D; Watling, R John

    2009-01-01

    The use of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been compared with the traditional method of refractive index (RI) measurement for the establishment of the provenance of glass bottles. Using the RI method alone, it is not possible to discriminate between certain glass bottles produced up to 18 days apart from a single manufacturing plant. Furthermore, variations in RI within a single bottle can be large enough to invalidate co-provenance establishment using this technique alone. Determination of the trace elemental composition of bottles collected over a 1-month period confirmed that minimal variation of trace metal distribution occurred within individual bottles made during this period. Therefore, the trace element composition of any fragment of glass from a broken bottle may be considered representative of the elemental composition of the entire bottle. In addition, statistical comparison of the distribution of approximately 38 of the 56 analytes that were determined established that it was possible to discriminate between two glass bottles manufactured in the same plant two hours apart. Using this methodology it has been possible to develop an analytical protocol to significantly improve the accurate comparison and provenance establishment of forensic glass evidence.

  5. A comparison of continuous pneumatic nebulization and flow injection-direct injection nebulization for sample introduction in inductively coupled plasma-mass spectrometry

    SciTech Connect

    Crain, J.S.; Kiely, J.T.

    1995-08-01

    Dilute nitric acid blanks and solutions containing Ni, Cd, Pb, and U (including two laboratory waste samples) were analyzed eighteen times over a two-month period using inductively coupled plasma-mass spectrometry (ICP-MS). Two different sample introduction techniques were employed: flow injection-direct injection nebulization (FI-DIN) and continuous pneumatic nebulization (CPN). Using comparable instrumental measurement procedures, FI-DIN analyses were 33% faster and generated 52% less waste than CPN analyses. Instrumental limits of detection obtained with FI-DIN and CPN were comparable but not equivalent (except in the case of Pb) because of nebulizer-related differences in sensitivity (i.e., signal per unit analyte concentration) and background. Substantial and statistically significant differences were found between FI-DIN and CPN Ni determinations, and in the case of the laboratory waste samples, there were also small but statistically significant differences between Cd determinations. These small (2 to 3%) differences were not related to polyatomic ion interference (e.g., {sup 95}Mo{sup 16}O{sup +}), but in light of the time savings and waste reduction to be realized, they should not preclude the use of FI-DIN in place of CPN for determination of Cd, Pb, U and chemically.

  6. A comparison of continuous pneumatic nebulization and flow injection-direction injection nebulization for sample introduction in inductively coupled plasma-mass spectrometry

    SciTech Connect

    Crain, J.S.; Kiely, J.T.

    1997-08-01

    Samples containing Ni, Cd, Pb, and U were analyzed eighteen times over a two-month period using inductively coupled plasma-mass spectrometry (ICP-MS). Sample introduction was accomplished by either flow injection-direct injection nebulization (FI-DIN) or continuous pneumatic nebulization (CPN). Using comparable instrumental measurement procedures, FI-DIN analyses were 33% faster and generated 52% less waste than CPN analyses. Instrumental limits of detection obtained with FI-DIN and CPN were comparable but not equivalent (except in the case of Pb) because of nebulizer-related differences in sensitivity (i.e., signal per unit analyte concentration) and background. Substantial and statistically significant differences were found between FI-DIN and CPN Ni determinations, and in the case of laboratory waste samples, there were also small but statistically significant differences between Cd determinations. These small (2 to 3%) differences were not related to polyatomic ion interference (e.g., {sup 95}Mo{sup 16}O{sup +}), but in light of the time and waste savings to be realized, they should not preclude the use of FI-DIN in place of CPN for determination of Cd, Pb, U, and similar elements present at trace concentrations.

  7. Determination of toxic inorganic elements pollution in ground waters of Kahuta Industrial Triangle Islamabad, Pakistan using inductively coupled plasma mass spectrometry.

    PubMed

    Kausar, Rubina; Ahmad, Zulfiqar

    2009-10-01

    The present study deals with the ground water quality assessment in Kahuta Industrial Triangle Islamabad, Pakistan. The objective of the study was to assess ground water quality against the drinking water standards for various toxic inorganic elements. Representative groundwater samples were collected and analyzed in the Water Quality Laboratory of Pakistan Council of Research in Water Resources (PCRWR) at Islamabad, Pakistan. The samples were run on ICP-MS (Inductively coupled plasma mass spectrometry), which has the capability to separate and quantify 70 elements at a time. One of the finding of study is that ICP-MS is a very good tool to analyze broad range of toxic inorganic elements to the level of parts per billion (ppb). World Health Organization drinking water standards shows that these toxic inorganic elements such as heavy metals even at this concentration level (ppb) are injurious to human health. This analysis indicated pollution of various toxic elements including Selenium. Vertical leachate through industrial waste septic tanks is identified as major cause of groundwater pollution in the Industrial Triangle. Monitoring of the septic tanks and groundwater quality in study area is suggested along with remedial measures.

  8. Multi-isotopic determination of plutonium (239Pu, 240Pu, 241Pu and 242Pu) in marine sediments using sector-field inductively coupled plasma mass spectrometry.

    PubMed

    Donard, O F X; Bruneau, F; Moldovan, M; Garraud, H; Epov, V N; Boust, D

    2007-03-28

    Among the transuranic elements present in the environment, plutonium isotopes are mainly attached to particles, and therefore they present a great interest for the study and modelling of particle transport in the marine environment. Except in the close vicinity of industrial sources, plutonium concentration in marine sediments is very low (from 10(-4) ng kg(-1) for (241)Pu to 10 ng kg(-1) for (239)Pu), and therefore the measurement of (238)Pu, (239)Pu, (240)Pu, (241)Pu and (242)Pu in sediments at such concentration level requires the use of very sensitive techniques. Moreover, sediment matrix contains huge amounts of mineral species, uranium and organic substances that must be removed before the determination of plutonium isotopes. Hence, an efficient sample preparation step is necessary prior to analysis. Within this work, a chemical procedure for the extraction, purification and pre-concentration of plutonium from marine sediments prior to sector-field inductively coupled plasma mass spectrometry (SF-ICP-MS) analysis has been optimized. The analytical method developed yields a pre-concentrated solution of plutonium from which (238)U and (241)Am have been removed, and which is suitable for the direct and simultaneous measurement of (239)Pu, (240)Pu, (241)Pu and (242)Pu by SF-ICP-MS.

  9. Determination of total iodine in infant formula and nutritional products by inductively coupled plasma/mass spectrometry: single-laboratory validation.

    PubMed

    Pacquette, Lawrence H; Levenson, Alan M; Thompson, Joseph J

    2012-01-01

    A single-laboratory validation by inductively coupled plasma-mass spectrometry was developed for the determination total iodine (m/z 127) in infant formula and adult nutritional products. All samples were digested in nitric acid using a closed vessel microwave oven system; Te (m/z 130) was used as an internal standard. To prevent loss of iodine, ammonium hydroxide solution was added to the samples immediately after digestion. The method quantitation limit for total iodine was 0.3 ng/mL, but a practical LOQ was used at 1.0 ng/mL, a concentration at which there was a negligible bias due to nonlinearity. The total iodine concentrations (112-1900 ng/g) in 14 out of 15 nutritional products were within specification limits. Within-day and day-to-day (6 independent days) precision values were < 10% RSD. The observed precision for the overall mean (18 independent days) of a control sample was approximately 4% RSD. In two National Institute of Standards and Technology standard reference materials, total iodine results were within certified limits. Sample spike recoveries for all 15 nutritional products were 92-105%. The data show that a conventional microwave oven digestion procedure can be used to prepare samples for iodine determination. Therefore, this technique is very compatible with other methods being proposed as modern official methods for the analysis of minerals in nutritional products.

  10. Monitoring of platinum in a single hair by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) after cisplatin treatment for cancer

    NASA Astrophysics Data System (ADS)

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

    2008-04-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to quantify and monitor the concentration of Pt along a single strand of hair from a patient who had been treated with cisplatin as cytostatic drug. The sensitivity of the analytical method developed could be increased by total ablation of the hair cross-section compared to partial ablationE A low-noise intensity ratio was obtained along the strand, while the blank was negligible. The variation of the Pt signal with reference to each cisplatin dose was clearly observed. Home-made standards consisting of Pt-enriched hair strands served as calibrators and sulphur (measuring 34S+) was used as the internal reference element. The correlation coefficient of the calibration curve for platinum was 0.9973 and the detection limit was 0.029 [mu]g g-1. The rate of hair growth between doses was constant. The mean relative standard deviation (R.S.D.) for five replicates of single hair strands ranged from 15 to 22%. The maximum concentrations of Pt found along the hair strands were 26.9 ± 5.3, 14.7 ± 3.3, 20.9 ± 3.9 and 26.1 ± 3.8 [mu]g g-1, which correspond to four treatment of cisplatin administered to the patient at 3-week intervals.

  11. Dithizone-functionalized solid phase extraction-displacement elution-high performance liquid chromatography-inductively coupled plasma mass spectrometry for mercury speciation in water samples.

    PubMed

    Yin, Yong-guang; Chen, Ming; Peng, Jin-feng; Liu, Jing-fu; Jiang, Gui-bin

    2010-06-15

    A novel and simple solid phase extraction (SPE)-high performance liquid chromatography (HPLC)-inductively coupled plasma mass spectrometry (ICP-MS) method was developed for determination of inorganic mercury (IHg), methylmercury MeHg and ethylmercury (EtHg) in water samples in the present work. The procedure involves pre-functionalization of the commercially available C18 SPE column with dithizone, loading water sample, displacement elution of mercury species by Na(2)S(2)O(3) solution, followed by HPLC-ICP-MS determination. Characterization and optimization of operation parameters of this new SPE procedure were discussed, including eluting reagent selection, concentration of eluting reagent, volume of eluting reagent, effect of NaCl and humic acid in sample matrix. At optimized conditions, the detection limits of mercury species for 100mL water sample were about 3ngL(-1) and the average recoveries were 93.7, 83.4, and 71.7% for MeHg, IHg and EtHg, respectively, by spiking 0.2microgL(-1) mercury species into de-ion water. Stability experiment reveals that both the dithizone-functionalized SPE cartridge and the mercury species incorporated were stable in the storage procedure. These results obtained demonstrate that SPE-HPLC-ICP-MS is a simple and sensitive technique for the determination of mercury species at trace level in water samples with high reproducibility and accuracy.

  12. Selenium speciation in animal tissues after enzymatic digestion by high-performance liquid chromatography coupled to inductively coupled plasma mass spectrometry.

    PubMed

    Quijano, M A; Moreno, P; Gutiérrez, A M; Pérez-Conde, M C; Cámara, C

    2000-07-01

    A procedure is described for the enzymatic digestion of tuna and mussel samples that allows the determination of selenium species by high-performance liquid chromatography in conjunction with inductively coupled plasma mass spectrometry. The species were extracted by two-step enzymatic hydrolysis with a non-specific protease (subtilisin). The selenium species were separated on a Spherisorb 5 ODS/AMINO column using two different chromatographic conditions, namely phosphate buffers at pH 2.8 and pH 6.0 as mobile phases. The method determines organic (trimethylselenonium, selenocystine, selenomethionine and selenoethionine) and inorganic selenium species (selenite and selenate), but only organic selenium species were found in the samples. The sum of identified selenium species in the sample was about 30% of the total selenium present in the enzymatic extract despite the fact that recoveries of total hydrolysed selenium were 93-102%. Trimethylselenonium ion and selenomethionine were found in both tuna and mussel samples and an unknown selenium species was also found in tuna samples.

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

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

  14. Simultaneous characterisation of silver nanoparticles and determination of dissolved silver in chicken meat subjected to in vitro human gastrointestinal digestion using single particle inductively coupled plasma mass spectrometry.

    PubMed

    Ramos, K; Ramos, L; Gómez-Gómez, M M

    2017-04-15

    In this study, a chicken meat containing AgNPs (candidate reference material Nanolyse 14) has been used as a model matrix to study the fate and behaviour of AgNPs upon oral ingestion following an in vitro model that included saliva, gastric and intestinal digestions. The behaviour of a 40nm AgNPs standard solution during the three digestion steps was also evaluated. Sample preparation conditions were optimised to prevent AgNPs oxidation and/or aggregation and to ensure the representativeness of the reported results. Total silver released from the test sample and the evaluated AgNP standard was determined by inductively coupled plasma mass spectrometry (ICPMS). The presence of both AgNPs and dissolved silver in the extracts was confirmed by single particle (SP)-ICPMS analysis. AgNPs were sized and the particle number concentration determined in the three digestion juices. Experimental results demonstrated differentiated behaviours for AgNP from the standard solution and the meat sample highlighting the relevance of using physiological conditions for accurate risk assessment. In the most realistic scenario assayed (i.e., spiked chicken meat analysis), only 13% of the AgNPs present in the reference material would reach the intestine wall. Meanwhile, other bioaccessible dissolved forms of silver would account for as much as 44% of the silver initially spiked to the meat paste.

  15. 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.

  16. Validation of an optimized method for the determination of iodine in human breast milk by inductively coupled plasma mass spectrometry (ICPMS) after tetramethylammonium hydroxide extraction.

    PubMed

    Huynh, Dao; Zhou, Shao Jia; Gibson, Robert; Palmer, Lyndon; Muhlhausler, Beverly

    2015-01-01

    In this study a novel method to determine iodine concentrations in human breast milk was developed and validated. The iodine was analyzed by inductively coupled plasma mass spectrometry (ICPMS) following tetramethylammonium hydroxide (TMAH) extraction at 90°C in disposable polypropylene tubes. While similar approaches have been used previously, this method adopted a shorter extraction time (1h vs. 3h) and used antimony (Sb) as the internal standard, which exhibited greater stability in breast milk and milk powder matrices compared to tellurium (Te). Method validation included: defining iodine linearity up to 200μgL(-1); confirming recovery of iodine from NIST 1549 milk powder. A recovery of 94-98% was also achieved for the NIST 1549 milk powder and human breast milk samples spiked with sodium iodide and thyroxine (T4) solutions. The method quantitation limit (MQL) for human breast milk was 1.6μgL(-1). The intra-assay and inter-assay coefficient of variation for the breast milk samples and NIST powder were <1% and <3.5%, respectively. NIST 1549 milk powder, human breast milk samples and calibration standards spiked with the internal standard were all stable for at least 2.5 months after extraction. The results of the validation process confirmed that this newly developed method provides greater accuracy and precision in the assessment of iodine concentrations in human breast milk than previous methods and therefore offers a more reliable approach for assessing iodine concentrations in human breast milk.

  17. Development of isotope dilution cold vapor inductively coupled plasma mass spectrometry and its application to the certification of mercury in NIST standard reference materials.

    PubMed

    Christopher, S J; Long, S E; Rearick, M S; Fassett, J D

    2001-05-15

    An isotope dilution cold vapor inductively coupled plasma mass spectrometry (ID-CV-ICPMS) method featuring gaseous introduction of mercury via tin chloride reduction has been developed and applied to the quantification and certification of mercury in various NIST standard reference materials: SRM 966 Toxic Metals in Bovine Blood (30 ng x mL(-1)); SRM 1641d Mercury in Water (1.6 microg x mL(-1)); and SRM 1946 Lake Superior Fish Tissue (436 ng x g(-1)). Complementary mercury data were generated for SRMs and NIST quality control standards using cold vapor atomic absorption spectroscopy (CVAAS). Certification results for the determination of mercury in SRM 1641d using two independent methods (ID-CV-ICPMS and CVAAS) showed a degree of agreement of 0.3% between the methods. Gaseous introduction of mercury into the ICPMS resulted in a single isotope sensitivity of 2 x 10(6) counts x s(-1)/ng x g(-1) for 201Hg and significantly reduced the memory and washout effects traditionally encountered in solution nebulization ICPMS. Figures of merit for isotope ratio accuracy and precision were evaluated at dwell times of 10, 20, 40, 80, and 160 ms using SRM 3133 Mercury Spectrometric Solution. The optimum dwell time of 80 ms yielded a measured 201Hg/202Hg isotope ratio within 0.13% of the theoretical natural value and a measurement precision of 0.34%, on the basis of three replicate injections of SRM 3133.

  18. Development of a novel low-flow ion source/sampling cone geometry for inductively coupled plasma mass spectrometry and application in hyphenated techniques

    NASA Astrophysics Data System (ADS)

    Pfeifer, Thorben; Janzen, Rasmus; Steingrobe, Tobias; Sperling, Michael; Franze, Bastian; Engelhard, Carsten; Buscher, Wolfgang

    2012-10-01

    A novel ion source/sampling cone device for inductively coupled plasma mass spectrometry (ICP-MS) especially operated in the hyphenated mode as a detection system coupled with different separation modules is presented. Its technical setup is described in detail. Its main feature is the very low total argon consumption of less than 1.5 L min- 1, leading to significant reduction of operational costs especially when time-consuming speciation analysis is performed. The figures of merit of the new system with respect to sensitivity, detection power, long-term stability and working range were explored. Despite the profound differences of argon consumption of the new system in comparison to the conventional ICP-MS system, many of the characteristic features of the conventional ICP-MS could be maintained to a great extent. To demonstrate the ion source's capabilities, it was used as an element-selective detector for gas (GC) and high performance liquid chromatography (HPLC) where organic compounds of mercury and cobalt, respectively, were separated and detected with the new low-flow ICP-MS detection system. The corresponding chromatograms are shown. The applicability for trace element analysis has been validated with the certified reference material NIST 1643e.

  19. Fast preconcentration of trace rare earth elements from environmental samples by di(2-ethylhexyl)phosphoric acid grafted magnetic nanoparticles followed by inductively coupled plasma mass spectrometry detection

    NASA Astrophysics Data System (ADS)

    Yan, Ping; He, Man; Chen, Beibei; Hu, Bin

    2017-10-01

    In this work, di(2-ethylhexyl)phosphoric acid (P204) grafted magnetic nanoparticles were synthesized by fabricating P204 onto Fe3O4@TiO2 nanoparticles based on Lewis acid-base interaction between Ti and phosphate group under weakly acidic condition. The prepared Fe3O4@TiO2@P204 nanoparticles exhibited excellent selectivity for rare earth elements, and good anti-interference ability. Based on it, a method of magnetic solid phase extraction (MSPE) combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for fast preconcentration and determination of trace rare earth elements in environmental samples. Under the optimal conditions, the detection limits of rare earth elements were in the range of 0.01 (Tm)-0.12 (Nd) ng L- 1 with an enrichment factor of 100-fold, and the relative standard deviations ranged from 4.9 (Pr) to 10.7% (Er). The proposed method was successfully applied to the determination of rare earth elements in environmental samples, including river water, lake water, seawater and sediment.

  20. 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.

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

    PubMed

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

    2015-12-01

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

  2. Simultaneous determination of arsenic and mercury species in rice by ion-pairing reversed phase chromatography with inductively coupled plasma mass spectrometry.

    PubMed

    Fang, Yong; Pan, Yushi; Li, Peng; Xue, Mei; Pei, Fei; Yang, Wenjian; Ma, Ning; Hu, Qiuhui

    2016-12-15

    An analytical method using reversed phase chromatography-inductively coupled plasma mass spectrometry for arsenic and mercury speciation analysis was described. The effect of ion-pairing reagent on simultaneous separation of four arsenic (arsenite, arsenate, monomethlyarsonate and dimethylarsinate) and three mercury species (inorganic mercury (Hg(II)), methylmecury and ethylmercury) was investigated. Parameters including concentrations and pH of the mobile phase were optimized. The separation and re-equilibration time was attained within 20min. Meanwhile, a sequential extraction method for arsenic and mercury in rice was tested. Subsequently, 1% HNO3 microwave-assisted extraction was chosen. Calibration curves based on peak area measurements were linear with correlation coefficient greater than 0.9958 for each species in the range studied. The detection limits of the species were in the range of 0.84-2.41μg/L for arsenic and 0.01-0.04μg/L for mercury, respectively. The proposed method was then successfully applied for the simultaneous determination of arsenic and mercury species in rice flour standard material and two kinds of rice from local markets. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    PubMed

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

    2014-12-10

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

  4. Effect of solvent type on the determination of total iodine in milk powder and human serum by inductively coupled plasma mass spectrometry.

    PubMed

    Vanhoe, H; Van Allemeersch, F; Versieck, J; Dams, R

    1993-08-01

    A method for the determination of the total iodine content in milk powder and human serum by inductively coupled plasma mass spectrometry is described. It is shown that the oxidation state of the analyte has a strong impact on the analytical performance. If iodine is present as iodide and nitric acid is used for acidification, the observed ion signal is not stable and samples spiked with iodide yield erroneous recoveries up to 750%. Hence, as the iodine in milk powder is present almost exclusively as iodide, destruction of the sample with nitric acid is not suitable. It was found that such an excessive spike recovery does not occur if ammonia solution instead of nitric acid is used as the diluent. The proposed sample preparation was tested by analysing three reference milk powders, namely Certified Reference Materials 150 and 151 Spiked Skim Milk Powder (from the Community Bureau of Reference) and Standard Reference Material 1549 Non-Fat Milk Powder (from the National Institute of Standards and Technology). Good agreement with the certified values was obtained, indicating that no significant errors are introduced. For human serum, samples treated with nitric acid or with ammonia solution gave results that were not significantly different from each other. Results are given for both a 'second-generation' biological reference material, Freeze-Dried Human Serum (University of Ghent), and for sera from healthy individuals.

  5. Characterization of colloidal arsenic at two abandoned gold mine sites in Nova Scotia, Canada, using asymmetric flow-field flow fractionation-inductively coupled plasma mass spectrometry.

    PubMed

    Tindale, Kathryn J; Patel, Pritesh J; Wallschläger, Dirk

    2016-11-01

    Asymmetric flow-field flow fractionation-inductively-coupled plasma-mass spectrometry was used to determine whether colloidal arsenic (As) exists in soil pore water and soil extract samples at two arsenic-contaminated abandoned gold mines (Montague and Goldenville, Nova Scotia). Colloidal arsenic was found in 12 out of the 80 collected samples (=15%), and was primarily associated with iron (Fe) in the encountered colloids. The molar Fe/As ratios indicate that the colloids in some samples appeared to be discrete iron-arsenic minerals, whereas in other samples, they were more consistent with As-rich iron (oxy)hydroxides. Up to three discrete size fractions of colloidal As were encountered in the samples, with mean colloid diameters between 6 and 14nm. The pore water samples only contained one size fraction of As-bearing colloids (around 6nm diameter), while larger As-bearing colloids were only encountered in soil extracts. Copyright © 2016. Published by Elsevier B.V.

  6. High spatial resolution quantitative imaging by cross-calibration using Laser Ablation Inductively Coupled Plasma Mass Spectrometry and Synchrotron micro-X-ray Fluorescence technique.

    PubMed

    Wang, Hao A O; Grolimund, Daniel; Van Loon, Luc R; Barmettler, Kurt D; Borca, Camelia N; Aeschlimann, Beat; Günther, Detlef

    2012-01-01

    High spatial resolution, quantitative chemical imaging is of importance to various scientific communities, however high spatial resolution and robust quantification are not trivial to attain at the same time. In order to achieve microscopic chemical imaging with enhanced quantification capabilities, the current study links the independent and complementary advantages of two micro-analytical techniques - Synchrotron Radiation-based micro X-ray Fluorescence (SR-microXRF) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS). A cross-calibration approach is established between these two techniques and validated by one experimental demonstration. In the presented test case, the diffusion pattern of trace level Cs migrating into a heterogeneous geological medium is imaged quantitatively with high spatial resolution. The one-dimensional line scans and the two-dimensional chemical images reveal two distinct types of geochemical domains: calcium carbonate rich domains and clay rich domains. During the diffusion, Cs shows a much higher interfacial reactivity within the clay rich domain, and turns out to be nearly non-reactive in the calcium carbonate domains. Such information obtained on the micrometer scale improves our chemical knowledge concerning reactive solute transport mechanism in heterogeneous media. Related to the chosen demonstration study, the outcome of the quantitative, microscopic chemical imaging contributes to a refined safety assessment of potential host rock materials for deep-geological nuclear waste storage repositories.

  7. Determination of traces of uranium and thorium in titanium and copper used for the construction of the Russian Emission Detector 100 by inductively coupled plasma mass spectrometry.

    PubMed

    Poteshin, Sergey S; Sysoev, Alexey A; Lagunov, Sergey S; Sereda, Andrei; Sosnovtsev, Valery V; Bolozdynya, Alexander I; Efremenko, Yuriy B

    2015-01-01

    The Russian Emission Detector 100 (RED-100) under construction at the National Research Nuclear University MEPhI (Moscow Engineering Physics Institute) is designed to detect the presently undiscovered effect of coherent neutrino scattering. One of the factors limiting the sensitivity of the detector is the spontaneous decay of uranium and thorium in the detector materials. Radioactive impurities in detector materials at levels of parts per billion can significantly affect the sensitivity. Five random samples of titanium and one of copper from materials used in the construction of the detector were selected for assay. The concentration of (232)Th and (238)U were measured by inductively coupled plasma mass spectrometry (ICP- MS) in solid titanium using both: solutions in acids and direct sampling by laser ablation (LA-ICP-MS). The LA- ICP-MS method allowed us to determine (238)U and (232)Th at subnanogram per gram levels. This method is much faster than ICP-MS with liquid injection. The titanium samples studied have impurities in the range between 1 ng g(-1) and 21 ng g(-1) for (238)U and 3 ng g(-1) and 31 ng g(-1) for (232)Th. In copper we set upper limits of 0.4 ng g(-1) for (238)U and 1 ng g(-1)for (232)Th. The total activity of the cryostat constructed from materials studied was estimated to be 43 Bq.

  8. Comparison of copper labeling followed by liquid chromatography-inductively coupled plasma mass spectrometry and immunochemical assays for serum hepcidin-25 determination.

    PubMed

    Konz, Tobias; Alonso-García, Javier; Montes-Bayón, María; Sanz-Medel, Alfredo

    2013-10-17

    Hepcidin-25 has been defined as the key biomarker in iron metabolism. This peptide binds to the iron transporter ferroportin to cause its degradation. Therefore, the need for specific, accurate and precise methods for the quantification of hepcidin-25 in biological fluids is dramatically increasing. In this regard, the use of rapid immunochemical methods that provide low limit of quantification is desired for routine clinical use. However, such fast methodologies should be first analytically evaluated and compared with alternative strategies to check for their advantages and limitations. Here we compare the use of a commercial immunochemical assay for hepcidin determination with a novel analytical approach based on Cu-labeling of the peptide followed by Cu determination using liquid chromatography (HPLC) and plasma mass spectrometry (ICP-MS). The figures of merit of both systems reveal similar analytical characteristics and both seem to be adequate for the determination of the peptide at biologically relevant concentrations in human serum samples. The analysis of a larger number of samples (n=50) by both techniques showed a good agreement in the concentrations found. Such finding permits to address the hepcidin recovery in the sample preparation procedure necessary for the HPLC-ICP-MS analysis in human serum that turn out to be 76-85%. Additionally, limitations due to cross-reactivity issues of the ELISA method could be addressed in some of the samples by using LC-ICP-MS and were confirmed by LC-Electrospray-MS. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. Improving Precision and Accuracy of Isotope Ratios from Short Transient Laser Ablation-Multicollector-Inductively Coupled Plasma Mass Spectrometry Signals: Application to Micrometer-Size Uranium Particles.

    PubMed

    Claverie, Fanny; Hubert, Amélie; Berail, Sylvain; Donard, Ariane; Pointurier, Fabien; Pécheyran, Christophe

    2016-04-19

    The isotope drift encountered on short transient signals measured by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) is related to differences in detector time responses. Faraday to Faraday and Faraday to ion counter time lags were determined and corrected using VBA data processing based on the synchronization of the isotope signals. The coefficient of determination of the linear fit between the two isotopes was selected as the best criterion to obtain accurate detector time lag. The procedure was applied to the analysis by laser ablation-MC-ICPMS of micrometer sized uranium particles (1-3.5 μm). Linear regression slope (LRS) (one isotope plotted over the other), point-by-point, and integration methods were tested to calculate the (235)U/(238)U and (234)U/(238)U ratios. Relative internal precisions of 0.86 to 1.7% and 1.2 to 2.4% were obtained for (235)U/(238)U and (234)U/(238)U, respectively, using LRS calculation, time lag, and mass bias corrections. A relative external precision of 2.1% was obtained for (235)U/(238)U ratios with good accuracy (relative difference with respect to the reference value below 1%).

  10. Polymer monolithic capillary microextraction on-line coupled with inductively coupled plasma-mass spectrometry for the determination of trace Au and Pd in biological samples

    NASA Astrophysics Data System (ADS)

    Liu, Xiaolan; He, Man; Chen, Beibei; Hu, Bin

    2014-11-01

    A novel method based on on-line polymer monolithic capillary microextraction (CME)-inductively coupled plasma mass spectrometry (ICP-MS) was developed for the determination of trace Au and Pd in biological samples. For this purpose, poly(glycidyl methacrylate-ethylene dimethacrylate) monolith was prepared and functionalized with mercapto groups. The prepared monolith exhibited good selectivity to Au and Pd, and good resistance to strong acid with a long life span. Factors affecting the extraction efficiency of CME, such as sample acidity, sample flow rate, eluent conditions and coexisting ion interference were investigated in detail. Under the optimal conditions, the limits of detection (LODs, 3σ) were 5.9 ng L- 1 for Au and 8.3 ng L- 1 for Pd, and the relative standard deviations (RSDs, c = 50 ng L -1, n = 7) were 6.5% for Au and 1.1% for Pd, respectively. The developed method was successfully applied to the determination of Au and Pd in human urine and serum samples with the recovery in the range of 84-118% for spiked samples. The developed on-line polymer monolithic CME-ICP-MS method has the advantages of rapidity, simplicity, low sample/reagent consumption, high sensitivity and is suitable for the determination of trace Au and Pd in biological samples with limited amount available and complex matrix.

  11. Metallomics for drug development: serum protein binding and analysis of an anticancer tris(8-quinolinolato)gallium(III) drug using inductively coupled plasma mass spectrometry.

    PubMed

    Ossipov, Konstantin; Foteeva, Lidia S; Seregina, Irina F; Perevalov, Sergei A; Timerbaev, Andrei R; Bolshov, Mikhail A

    2013-06-27

    The application of an inductively coupled plasma mass spectrometry (ICP-MS) assay for quantifying in vitro binding of a gallium-based anticancer drug, tris(8-quinolinolato)gallium(III), to serum albumin and transferrin and in human serum is described. The distribution of the drug between the protein-rich and protein-free fractions was assessed via ICP-MS measurement of total gallium in ultrafiltrates. Comparative kinetic studies revealed that the drug exhibits a different reactivity toward individual proteins. While the maximum possible binding to albumin (~10%) occurs practically immediately, interaction with transferrin has a step-like character and the equilibrium state (with more than 50% binding) is reached for about 48 h. Drug transformation into the bound form in serum, also very fast, results in almost quantitative binding (~95%). The relative affinity of protein-drug binding was characterized in terms of the association constants ranging from 10(3) to 10(4)M(-1). In order to further promote clinical testing of the gallium drug, the ICP-MS method was applied for direct quantification of gallium in human serum spiked with the drug. The detection limit for gallium was found to be as low as 20 ng L(-1). The repeatability was better than 8% (as RSD) and the achieved recoveries were in the range 99-103%. Copyright © 2013 Elsevier B.V. All rights reserved.

  12. Ion chromatography/inductively coupled plasma mass spectrometry for simultaneous determination of glyphosate, glufosinate, fosamine and ethephon at nanogram levels in water.

    PubMed

    Guo, Zhong-Xian; Cai, Qiantao; Yang, Zhaoguang

    2007-01-01

    This paper describes the first approach that simultaneously quantifies four polar, water-soluble organophosphorus herbicides, i.e., glyphosate, glufosinate, fosamine and ethephon, at nanogram levels in environmental waters. The target herbicides were separated completely by ion chromatography (IC) on a polymer anion-exchange column, Dionex IonPac AS16 (4.0 mm x 250 mm), with 30 mM citric acid flowing at 0.70 mL min(-1) as the eluent. On-line inductively coupled plasma mass spectrometry (ICP-MS) using a quadrupole mass spectrometer was employed as a sensitive and selective detector of the effluents. Various parameters affecting the separation and detection were systematically examined and optimized. Detection limits of the herbicides achieved with the proposed IC/ICP-MS method were 1.1-1.4 microg L(-1) (as compound) based on a 500-microL sample injection. Matrix anions, metal ions, phosphate, polyphosphates, non-polar and other polar organophosphorus pesticides showed no interference. The developed method was validated using reservoir water, treated water and NEWater samples spiked at the level of 10-25 microg L(-1) with satisfactory recoveries (95-109%). It is applicable to the simultaneous determination of microg L(-1) concentrations of the herbicides in polluted water.

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

    PubMed

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

    2012-08-15

    Analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) for determination of lanthanides in plant materials was investigated and compared with neutron activation analysis (NAA) as well as ion chromatography (IC) with UV-VIS detection. Two sample preparation protocols were tested: (i) microwave assisted digestion by concentrated nitric acid; (ii) microwave digestion involving silica and fluoride removal, followed by the selective and quantitative lanthanides group separation from the plant matrix. Several Certified Reference Materials (CRM) of plant origin were used for the evaluation of the accuracy of the applied analytical procedures. The consistency of results, obtained by various methods, enabled to establish the tentative recommended values (TRV) for several missing elements in one of CRMs. The ICP-MS, due to its very high sensitivity, has the potential to contribute to this aim. The discrepancy of the results obtained by various methods was discussed in a view of possible matrix effects related to the composition of investigated materials. Copyright © 2012 Elsevier B.V. All rights reserved.

  14. Split Flow Online Solid-Phase Extraction Coupled with Inductively Coupled Plasma Mass Spectrometry System for One-Shot Data Acquisition of Quantification and Recovery Efficiency.

    PubMed

    Furukawa, Makoto; Takagai, Yoshitaka

    2016-10-04

    Online solid-phase extraction (SPE) coupled with inductively coupled plasma mass spectrometry (ICPMS) is a useful tool in automatic sequential analysis. However, it cannot simultaneously quantify the analytical targets and their recovery percentages (R%) in one-shot samples. We propose a system that simultaneously acquires both data in a single sample injection. The main flowline of the online solid-phase extraction is divided into main and split flows. The split flow line (i.e., bypass line), which circumvents the SPE column, was placed on the main flow line. Under program-controlled switching of the automatic valve, the ICPMS sequentially measures the targets in a sample before and after column preconcentration and determines the target concentrations and the R% on the SPE column. This paper describes the system development and two demonstrations to exhibit the analytical significance, i.e., the ultratrace amounts of radioactive strontium ((90)Sr) using commercial Sr-trap resin and multielement adsorbability on the SPE column. This system is applicable to other flow analyses and detectors in online solid phase extraction.

  15. Validation of the determination of the B isotopic composition in Roman glasses with laser ablation multi-collector inductively coupled plasma-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Devulder, Veerle; Gerdes, Axel; Vanhaecke, Frank; Degryse, Patrick

    2015-03-01

    The applicability of laser ablation multi-collector inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) for the determination of the B isotopic composition in Roman glasses was investigated. The δ11B values thus obtained provide information on the natron flux used during the glass-making process. The glass samples used for this purpose were previously characterized using pneumatic nebulization (PN) MC-ICP-MS. Unfortunately, this method is time-consuming and labor-intensive and consumes some 100 mg of sample, which is a rather high amount for ancient materials. Therefore, the use of the less invasive and faster LA-MC-ICP-MS approach was explored. In this work, the results for 29 Roman glasses and 4 home-made glasses obtained using both techniques were compared to assess the suitability of LA-MC-ICP-MS in this context. The results are in excellent agreement within experimental uncertainty. No difference in overall mass discrimination was observed between the Roman glasses, NIST SRM 610 reference glass and B6 obsidian. The expanded uncertainty of the LA-MC-ICP-MS approach was estimated to be < 2‰, which is similar to that obtained upon sample digestion and PN-MC-ICP-MS measurement.

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

    SciTech Connect

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

    2008-03-01

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

  17. Theoretical investigation of small polyatomic ions observed in inductively coupled plasma mass spectrometry: H(x)CO+ and H(x)N2(+) (x = 1, 2, 3).

    PubMed

    Sears, Kyle C; Ferguson, Jill W; Dudley, Timothy J; Houk, R S; Gordon, Mark S

    2008-03-27

    Two series of small polyatomic ions, HxCO+ and HxN2(+) (x = 1, 2, 3), were systematically characterized using three correlated theoretical techniques: density functional theory using the B3LYP functional, spin-restricted second-order perturbation theory, and singles + doubles coupled cluster theory with perturbative triples. On the basis of thermodynamic data, the existence of these ions in inductively coupled plasma mass spectrometry (ICP-MS) experiments is not surprising since the ions are predicted to be considerably more stable than their corresponding dissociation products (by 30-170 kcal/mol). While each pair of isoelectronic ions exhibit very similar thermodynamic and kinetic characteristics, there are significant differences within each series. While the mechanism for dissociation of the larger ions occurs through hydrogen abstraction, the triatomic ions (HCO+ and HN2(+)) appear to dissociate by proton abstraction. These differing mechanisms help to explain large differences in the abundances of HN2(+) and HCO+ observed in ICP-MS experiments.

  18. Speciation of glyphosate, phosphate and aminomethylphosphonic acid in soil extracts by ion chromatography with inductively coupled plasma mass spectrometry with an octopole reaction system.

    PubMed

    Chen, Zuliang; He, Wenxiang; Beer, Michael; Megharaj, Mallavarapu; Naidu, Ravendra

    2009-05-15

    Ion-pairing chromatography coupled with inductively coupled plasma mass spectrometry (ICP-MS) used for the speciation of phosphorus is limited as the mobile phase containing organic solvents changes in detection sensitivity and the carbon precipitates on torch and cones. To address this issue, anion-exchange chromatography with ICP-MS has been used for the speciation of glyphosate, phosphate and aminomethylphosphonic acid in soil extracts. The separation of the targets on a new column was achieved within 5 min using an eluent containing 20 mM NH(4)NO(3) at pH 5.1. Furthermore, since the polyatomic ions such as (14)N(16)O(1)H(+) and (15)N(16)O(+) from a nitrogen-based ion-pairing reagent interfered with ICP-MS detection of (31)P, an octopole reaction system was investigated to determine whether the polyatomic interferences could be reduced. The results show that addition of He to the cell can benefit analyses by reducing such interferences, but at the expense of reduced sensitivity. The detection limits in the range of 1.0-1.5 microg L(-1) (expressed as P) was achieved when 50 microL was injected using He as the collusion gas.

  19. Comparative Study of Metal Quantification in Neurological Tissue Using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Imaging and X-ray Fluorescence Microscopy.

    PubMed

    Davies, Katherine M; Hare, Dominic J; Bohic, Sylvain; James, Simon A; Billings, Jessica L; Finkelstein, David I; Doble, Philip A; Double, Kay L

    2015-07-07

    Redox-active metals in the brain mediate numerous biochemical processes and are also implicated in a number of neurodegenerative diseases. A number of different approaches are available for quantitatively measuring the spatial distribution of biometals at an image resolution approaching the subcellular level. Measured biometal levels obtained using laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS; spatial resolution 15 μm × 15 μm) were within the range of those obtained using X-ray fluorescence microscopy (XFM; spatial resolution 2 μm × 7 μm) and regional changes in metal concentration across discrete brain regions were replicated to the same degree. Both techniques are well suited to profiling changes in regional biometal distribution between healthy and diseased brain tissues, but absolute quantitation of metal levels varied significantly between methods, depending on the metal of interest. Where all possible variables affect metal levels, independent of a treatment/phenotype are controlled, either method is suitable for examining differences between experimental groups, though, as with any method for imaging post mortem brain tissue, care should be taken when interpreting the total metal levels with regard to physiological concentrations.

  20. A magnesium hydroxide preconcentration/matrix reduction method for the analysis of rare earth elements in water samples using laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Hsieh, Hui-Fang; Chen, Yi-Hsiang; Wang, Chu-Fang

    2011-08-15

    This paper describes a simple method for simultaneous preconcentration and matrix reduction during the analysis of rare earth elements (REEs) in water samples through laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). From a systematic investigation of the co-precipitation of REEs using magnesium hydroxide, we optimized the effects of several parameters - the pH, the amount of magnesium, the shaking time, the efficiency of Ba removal, and the sample matrix - to ensure quantitative recoveries. We employed repetitive laser ablation to remove the dried-droplet samples from the filter medium and introduce them into the ICP-MS system for determinations of REEs. The enrichment factors ranged from 8 to 88. The detection limit, at an enrichment factor of 32, ranged from 0.03 to 0.20 pg mL(-1). The relative standard deviations for the determination of REEs at a concentration of 1 ng mL(-1) when processing 40 mL sample solution were 2.0-4.8%. We applied this method to the satisfactory determination of REEs in lake water and synthetic seawater samples.

  1. Quantitative imaging of 2 nm monolayer-protected gold nanoparticle distributions in tissues using laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS).

    PubMed

    Elci, S Gokhan; Yan, Bo; Kim, Sung Tae; Saha, Krishnendu; Jiang, Ying; Klemmer, Gunnar A; Moyano, Daniel F; Tonga, Gulen Yesilbag; Rotello, Vincent M; Vachet, Richard W

    2016-04-21

    Functionalized gold nanoparticles (AuNPs) have unique properties that make them important biomedical materials. Optimal use of these materials, though, requires an understanding of their fate in vivo. Here we describe the use of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to image the biodistributions of AuNPs in tissues from mice intravenously injected with AuNPs. We demonstrate for the first time that the distributions of very small (∼2 nm core) monolayer-protected AuNPs can be imaged in animal tissues at concentrations in the low parts-per-billion range. Moreover, the LA-ICP-MS images reveal that the monolayer coatings on the injected AuNPs influence their distributions, suggesting that the AuNPs remain intact in vivo and their surface chemistry influences how they interact with different organs. We also demonstrate that quantitative images of the AuNPs can be generated when the appropriate tissue homogenates are chosen for matrix matching. Overall, these results demonstrate the utility of LA-ICP-MS for tracking the fate of biomedically-relevant AuNPs in vivo, facilitating the design of improved AuNP-based therapeutics.

  2. Multiplexed quantification of plant thylakoid proteins on Western blots using lanthanide-labeled antibodies and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

    PubMed

    de Bang, Thomas Christian; Pedas, Pai; Schjoerring, Jan Kofod; Jensen, Poul Erik; Husted, Søren

    2013-05-21

    We have developed a novel calibration method that allows concurrent quantification of multiple proteins by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) after Western blotting. Calibrants were made of nitrocellulose membranes doped with lanthanide standards. Excellent linearity was obtained in the interval from 0 to 24 ng lanthanide cm(-2). Cerium-labeled lysozyme was introduced as an internal reference protein, enabling correction for up to 50% difference in transfer efficiency during the blotting of membranes. The sensitivity of the LA-ICP-MS method was comparable to state-of-the-art chemiluminescence detection and was further improved by a factor of 20, using a polymer tag. Our method allowed reproducible and multiplexed quantification of five thylakoid proteins extracted from chloroplasts of the plant species Arabidopsis thaliana (relative standard deviation (RSD) of ≤ 5% in three independent analytical series). The method was capable of measuring the L subunit in photosystem I of an Arabidopsis mutant containing <5% of this particular protein, relative to the wild type. We conclude that the developed calibration method is highly suited for multiplexed and comparative protein studies, allowing for intermembrane comparisons with high sensitivity and reproducibility.

  3. Soluble arsenic and selenium species in fly ash/organic waste-amended soils using ion chromatography-inductively coupled plasma mass spectrometry

    SciTech Connect

    Jackson, B.P.; Miller, W.P.

    1999-01-15

    Mixing coal fly ash with an organic waste increases macronutrient content and may make land application of fly ash a viable disposal alternative. However, trace element chemistry of these mixed waste products warrants investigation. Speciation of As and Se in soil solutions of fly ash-, poultry litter- and sewage sludge-amended soils was determined over a 10-day period by ion chromatography coupled to inductively coupled plasma mass spectrometry (IC-ICP-MS). Detection limits were 0.031, 0.028, 0.051, 0.161, 0.497, and 0.660 {micro}g L{sup {minus}1} for dimethylarsinate (DMA), As(III), monomethylarsonate (MMA), As(V), Se(IV), and Se(VI), respectively. Arsenic was highly water-soluble from poultry litter and appeared to be predominantly As(V). Arsenic(V) was the predominant species in soil amended with two fly ashes. Application of fly ash/poultry litter mixtures increased As solubility and led to the prevalence of DMA as the major As species. DMA concentrations of these soil solutions decreased rapidly over the sampling period relative to As(V), suggesting that DMA readily underwent mineralization in the soil solution. Se(VI) was the predominant soluble Se species in all treatments indicating rapid oxidation of Se(IV) initially solubilized from the fly ashes.

  4. [Simultaneous determination of 7 arsenic species in chicken muscle and chicken liver with high performance liquid chromatography-inductively coupled plasma mass spectrometry].

    PubMed

    Yang, Lijun; Hu, Qiaoru; Guo, Wei; Liu, Yumin; Song, Xiaohua; Zhang, Pengcheng

    2011-05-01

    A method for the simultaneous determination of 7 arsenic species was developed with high performance liquid chromatography and inductively coupled plasma mass spectrometry (HPLC-ICP-MS). The sample was extracted with artificial gastric juice. The HPLC separation was performed on an anion analytical column utilizing a gradient elution program of ammonium carbonate and water as the mobile phase. Identification and quantification were achieved by ICP-MS. Good linearities of 7 arsenic species were observed in the range from 1 microg/kg to 50 microg/kg with the correlation coefficients greater than 0.999. The average recoveries of 7 arsenic species spiked at the three levels of 1, 2 and 10 microg/kg ranged from 84.3% to 106.6% with the relative standard deviations of 1.4%-4.2%. The quantification limits of 7 arsenic species were 1 microg/kg. The method was proved to be good reproducibility, high sensitivity and simple preprocessing. This method is suitable for the simultaneous determination of 7 arsenic species in chicken muscle and chicken liver.

  5. Method validation for determination of arsenic, cadmium, chromium and lead in milk by means of dynamic reaction cell inductively coupled plasma mass spectrometry.

    PubMed

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

    2008-08-22

    With Regulation No. 1881/2006 the European Union fixed a maximum level for lead in milk. Consequently, there is the need to determine very low concentration of elements that may be present in milk in trace and ultratrace levels. Quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) combined with dynamic reaction cell (DRC) has been widely employed in order to reach very low concentration, requested for this product. Furthermore, the DRC technology can help in removing polyatomic and argon-based interferences. In the present study, a method for the determination of arsenic, cadmium, chromium and lead in bovine milk was validated according to the EU common standards by means of DRC-ICP-MS. The main parameters evaluated in the validation were: recovery, repeatability and within-laboratory reproducibility, detection and quantification limits, linearity range and measurement uncertainty. Additionally, stability studies of the analyte in solution and ruggedness studies were carried out. The results obtained for limit of detection (LoD) and limit of quantification (LoQ) in microg kg(-1) were respectively: As, 3.1 and 9.5; Cd, 0.08 and 0.24; Cr, 0.229 and 0.693; Pb, 0.5 and 1.5. While for the recovery: As, 91%; Cd 96%; Cr 99%; Pb, 95%. As for the repeatability: As, 7%; Cd, 3%; Cr, 6%; Pb, 4%.

  6. Determination of chromium(III) and total chromium in seawater by on-line column preconcentration inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Hirata, Shizuko; Honda, Kazuto; Shikino, Osamu; Maekawa, Norihiro; Aihara, Masato

    2000-07-01

    An automated low-pressure flow injection method with on-line column preconcentration using inductively coupled plasma mass spectrometry is described for the determination of chromium(III) and total chromium in seawater. A home-made column of commercially available iminodiacetate resin, Muromac A-1, was used to concentrate chromium(III) in seawater at a pH of 3.0. Following washing of the column with water, the chromium(III) was eluted and transferred to the plasma with 0.70 M nitric acid. Total chromium was determined after the reduction of chromium(VI) to chromium(III) with a 2-mM hydroxylamine solution at pH 1.8. Detection limit (three times the relative standard deviation of the background) of chromium(III) in the artificial seawater based on eight replicate measurements was 0.020 ng ml -1 with a sample loading time of 120 s. The precision was ±1.9%. One sample can be processed in 5 min. Calibration was accomplished by means of artificial seawater. The proposed method was verified by the analysis of two Reference Standard Materials of seawater NASS-4 and CASS-3.

  7. Quantifying the Cellular Uptake of Antibody-Conjugated Au Nanocages by Two-Photon Microscopy and Inductively Coupled Plasma Mass Spectrometry

    PubMed Central

    Au, Leslie; Zhang, Qiang; Cobley, Claire M.; Gidding, Michael; Schwartz, Andrea G.; Chen, Jingyi; Xia, Younan

    2009-01-01

    Gold nanocages with localized surface plasmon resonance peaks in the near-infrared region exhibited a broad two-photon photoluminescence band extending from 450 to 650 nm when excited by a Ti:sapphire laser at 800 nm. The bright luminescence makes it possible to explore the use of Au nanocages as a new class of optical imaging agents for two-photon microscopy. In this work, we have demonstrated the use of two-photon microscopy as a convenient tool to directly examine the uptake of antibody-conjugated and PEGylated Au nanocages by U87MGwtEGFR cells. We have also correlated the results from two-photon microscopy with the data obtained by inductively coupled plasma mass spectrometry. Combined together, these results indicate that the antibody-conjugated Au nanocages were attached to the surface of the cells through antibody-antigen binding and then internalized into the cells via receptor-mediated endocytosis. The cellular uptake process was dependent on a number of parameters, including incubation time, incubation temperature, size of the Au nanocages, and the number of antibodies immobilized on each nanocage. PMID:19954236

  8. Fast Determination of Toxic Arsenic Species in Food Samples Using Narrow-bore High-Performance Liquid-Chromatography Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Terol, Amanda; Marcinkowska, Monika; Ardini, Francisco; Grotti, Marco

    2016-01-01

    A new method for the speciation analysis of arsenic in food using narrow-bore high-performance liquid-chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS) has been developed. Fast separation of arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid was carried out in 7 min using an anion-exchange narrow-bore Nucleosil 100 SB column and 12 mM ammonium dihydrogen phosphate of pH 5.2 as the mobile phase, at a flow rate of 0.3 mL min(-1). A PFA-ST micronebulizer jointed to a cyclonic spray chamber was used for HPLC-ICP-MS coupling. Compared with standard-bore HPLC-ICP-MS, the new method has provided higher sensitivity, reduced mobile-phase consumption, a lower matrix plasma load and a shorter analysis time. The achieved instrumental limits of detection were in the 0.3 - 0.4 ng As mL(-1) range, and the precision was better than 3%. The arsenic compounds were efficiently (>80%) extracted from various food samples using a 1:5 methanol/water solution, with additional ultrasonic treatment for rice products. The applicability of this method was demonstrated by the analysis of several samples, such as seafood (fish, mussels, shrimps, edible algae) and rice-based products (Jasmine and Arborio rice, spaghetti, flour, crackers), including three certified reference materials.

  9. Microwave dissolution of plant tissue and the subsequent determination of trace lanthanide and actinide elements by inductively coupled plasma-mass spectrometry

    SciTech Connect

    Alvarado, J.S.; Neal, T.J.; Smith, L.L.; Erickson, M.D.

    1997-08-01

    Recently there has been much concern with the ability of plants to uptake heavy metals from their surroundings. With the development of instrumental techniques with low detection limits such as inductively coupled plasma-mass spectrometry (ICP-MS), attention is shifting toward achieving faster and more elegant ways of oxidizing the organic material inherent in environmental samples. Closed-vessel microwave dissolution was compared with conventional methods for the determination of concentrations of cerium, samarium, europium, terbium, uranium and thorium in a series of samples from the National Institute of Standards and Technology and from fields in Idaho. The ICP-MS technique exhibited detection limits in parts-per-trillion and linear calibration plots over three orders of magnitude for the elements under study. The results obtained by using nitric acid and hydrogen peroxide in a microwave digestion system for the analysis of reference materials showed close agreement with the accepted values. These values were compared with results obtained from dry- and wet-ashing procedures. The findings from an experiment comparing radiometric techniques for the determination of actinide elements to ICP-MS are reported.

  10. Determination of mercury compounds in fish by microwave-assisted extraction and liquid chromatography-vapor generation-inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Chiou, Chwei-Sheng; Jiang, Shiuh-Jen; Kumar Danadurai, K. Suresh

    2001-07-01

    A method employing a vapor generation system and LC combined with inductively coupled plasma mass spectrometry (LC-ICP-MS) is presented for the determination of mercury in biological tissues. An open vessel microwave digestion system was used to extract the mercury compounds from the sample matrix. The efficiency of the mobile phase, a mixture of L-cysteine and 2-mercaptoethanol, was evaluated for LC separation of inorganic mercury [Hg(II)], methylmercury (methyl-Hg) and ethylmercury (ethyl-Hg). The sensitivity, detection limits and repeatability of the liquid chromatography (LC) ICP-MS system with a vapor generator were comparable to, or better than, that of an LC-ICP-MS system with conventional pneumatic nebulization, or other sample introduction techniques. The experimental detection limits for various mercury species were in the range of 0.05-0.09 ng ml -1 Hg, based on peak height. The proposed method was successfully applied to the determination of mercury compounds in a swordfish sample purchased from the local market. The accuracy of the method was evaluated by analyzing a marine biological certified reference material (DORM-2, NRCC).

  11. Arsenic speciation in rice by capillary electrophoresis/inductively coupled plasma mass spectrometry: enzyme-assisted water-phase microwave digestion.

    PubMed

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

    2015-04-01

    We report an analytical methodology for the quantification of common arsenic species in rice and rice cereal using capillary electrophoresis coupled with inductively coupled plasma mass spectrometry (CE-ICPMS). An enzyme (i.e., α-amylase)-assisted water-phase microwave extraction procedure was used to extract four common arsenic species, including dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), arsenite [As(III)], and arsenate [As(V)] from the rice matrices. The addition of the enzyme α-amylase during the extraction process was necessary to reduce the sample viscosity, which subsequently increased the injection volume and enhanced the signal response. o-Arsanilic acid (o-ASA) was added to the sample solution as a mobility marker and internal standard. The obtained repeatability [i.e., relative standard deviation (RSD %)] of the four arsenic analytes of interest was less than 1.23% for elution time and 2.91% for peak area. The detection limits were determined to be 0.15-0.27 ng g(-1). Rice standard reference materials SRM 1568b and CRM 7503-a were used to validate this method. The quantitative concentrations of each organic arsenic and summed inorganic arsenic were found within 5% difference of the certified values of the two reference materials.

  12. Evaluation of Dietary Supplement Contamination by Xenobiotic and Essential Elements Using Microwave-Enhanced Sample Digestion and Inductively Coupled Plasma-Mass Spectrometry.

    PubMed

    Zinn, Gregory M; Rahman, G M Mizanur; Faber, Scott; Wolle, Mesay Mulugeta; Pamuku, Matt; Kingston, H M Skip

    2016-01-01

    Dietary supplements were analyzed by evaluating the elemental content in six widely consumed products manufactured by four well-known companies. The elements included the neurotoxic and carcinogenic elements cadmium, mercury, aluminum, lead, arsenic, and antimony, as well as the essential elements zinc, selenium, chromium, iron, and copper, which were often not listed as ingredients on the product labels. Contamination from either xenobiotic or essential elements was found in all samples analyzed. The samples were prepared using US Environmental Protection Agency (EPA) Method 3052, microwave-enhanced digestion. The resulting digests were analyzed by Inductively Coupled Plasma-Mass Spectrometry based on EPA Method 6020B. The analytical protocols were validated by analyzing a multivitamin standard reference material, the National Institute of Standards and Technology Standard Reference Material 3280. The application of EPA standard methods demonstrated their utility in making accurate and precise measurements in complex matrices with multiple ingredients and excipients. In the future, the use of these methods could provide a uniform quality assurance protocol that can be implemented along with other industry guidelines to improve the production of dietary supplements.

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

    PubMed

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

    2012-03-01

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

  14. Evaluation of the Forensic Utility of Scanning Electron Microscopy-Energy Dispersive Spectroscopy and Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry for Printing Ink Examinations.

    PubMed

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

    2016-05-01

    Improvements in printing technology have exacerbated the problem of document counterfeiting, prompting the need for analytical techniques that better characterize inks for forensic analysis and comparisons. In this study, 319 printing inks (toner, inkjet, offset, and Intaglio) were analyzed directly on the paper substrate using scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS). As anticipated, the high sensitivity of LA-ICP-MS pairwise comparisons resulted in excellent discrimination (average of ~ 99.6%) between different ink samples from each of the four ink types and almost 100% correct associations between ink samples known to originate from the same source. SEM-EDS analysis also resulted in very good discrimination for different toner and intaglio inks (>97%) and 100% correct association for samples from the same source. SEM-EDS provided complementary information to LA-ICP-MS for certain ink types but showed limited utility for the discrimination of inkjet and offset inks.

  15. Analysis of solids by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS)—II. Matching with a pressed pellet

    NASA Astrophysics Data System (ADS)

    Van Heuzen, A. A.; Morsink, J. B. W.

    The possibility of quantitative elemental analysis of solids by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) has been investigated. The solids were mixed with binder material in a ratio of 1:10 and pressed into a pellet in order to obtain a similar matrix composition (matrix matching), and further so that an internal standard could be added. The binder material used was a 1:1 mixture of graphite and cellulose, the latter being impregnated with an aqueous palladium standard solution. The method was applied to various types of reference materials, including organic materials (leaves and grass), coal, fly ash and several geological materials. Though with the internal standard a precision of 3-6% relative could be obtained, matrix matching was not completely satisfactory. For all the reference materials, results were generally within a factor of 5 of the reference values. This proved to be independent of the mode of the laser (free-running or Q-switched), the elements studied (over 50) and the sample materials investigated. The detection limits obtained ranged from mg/kg levels for the lower mass elements to 1-100 μg/kg for the higher mass elements. However, the experimental set-up was subject to large memory effects. Detection limits estimated to be ultimately attainable if the memory effects can be overcome are a factor of 10-100 better.

  16. In situ trace-element analysis of individual silicate melt inclusions by laser ablation microprobe-inductively coupled plasma-mass spectrometry (LAM-ICP-MS)

    NASA Astrophysics Data System (ADS)

    Taylor, R. P.; Jackson, S. E.; Longerich, H. P.; Webster, J. D.

    1997-07-01

    This paper reports the successful application of laser ablation microprobe-inductively coupled plasma-mass spectrometry (LAM-ICP-MS) to the in situ analysis of a diverse suite of twenty trace elements including Zr, Hf, Nb, Ta, Y, and REEs, in individual silicate melt inclusions in phenocrysts from Fantale volcano, Ethiopia. The UV laser, a frequency quadrupled Nd: YAG operating at 266 nm, significantly improves the ablation characteristics of minerals that do not absorb strongly at near-IR wavelengths (e.g., quartz and feldspar). Furthermore, it allows for a significant reduction in ablation pit size to ca. 10 μm, thereby permitting numerous applications that require high-resolution sampling. Multiple ablations in individual melt inclusions in the size range 10-50 μm demonstrate both the effectiveness of the technique and the generally homogeneous character of the inclusions. Comparison of the LAM-ICP-MS data for international reference material RGM-1 (a rhyolite), with recommended values, indicates an analytical precision of <10% for most of the trace elements determined in this study. The trace element abundances of the Fantale melt inclusions, determined by LAM-ICP-MS, are typical of those of pantellerites (i.e., peralkaline rhyolites), and are consistent with their origin as tiny volumes of melt trapped in quartz and alkali-feldspar phenocrysts during the final stage of fractional crystallization of the host peralkaline magma.

  17. On-line isotope dilution in laser ablation inductively coupled plasma mass spectrometry using a microflow nebulizer inserted in the laser ablation chamber

    NASA Astrophysics Data System (ADS)

    Pickhardt, Carola; Izmer, Andrej V.; Zoriy, Miroslav V.; Schaumlöffel, D.; Sabine Becker, J.

    2006-02-01

    Laser ablation ICP-MS (inductively coupled plasma mass spectrometry) is becoming one of the most important analytical techniques for fast determination of trace impurities in solid samples. Quantification of analytical results requires matrix-matched standards, which are in some cases (e.g., high-purity metals, proteins separated by 2D gel electrophoresis) difficult to obtain or prepare. In order to overcome the quantification problem a special arrangement for on-line solution-based calibration has been proposed in laser ablation ICP-MS by the insertion of a microflow nebulizer in the laser ablation chamber. This arrangement allows an easy, accurate and precise quantification by on-line isotope dilution using a defined standard solution with an isotope enriched tracer nebulized to the laser-ablated sample material. An ideal matrix matching in LA-ICP-MS is therefore obtained during the measurement. The figures of merit of this arrangement with a microflow nebulizer inserted in the laser ablation chamber and applications of on-line isotope dilution in LA-ICP-MS on two different types of sample material (NIST glass SRM 612 and NIST apple leaves SRM 1515) will be described.

  18. Method for the quantification of vanadyl porphyrins in fractions of crude oils by High Performance Liquid Chromatography-Flow Injection-Inductively Coupled Plasma Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Wandekoken, Flávia G.; Duyck, Christiane B.; Fonseca, Teresa C. O.; Saint'Pierre, Tatiana D.

    2016-05-01

    High performance liquid chromatography hyphenated by flow injection to inductively coupled plasma mass spectrometry (HPLC-FI-ICP-MS) was used to investigate V linked to porphyrins present in fractions of crude oil. First, the crude oil sample was submitted to fractionation by preparative liquid chromatography with UV detection, at the porphyrin Soret band wavelength (400 nm). The obtained porphyrin fractions were then separated in a 250 mm single column, in the HPLC, and eluted with different mobile phases (methanol or methanol:toluene (80:20; v:v)). The quantification of V-porphyrins in the fractions eluted from HPLC was carried out by online measuring the 51V isotope in the ICP-MS, against vanadyl octaethylporphine standard solutions (VO-OEP), prepared in the same solvent as the mobile phase, and injected post-column directly into the plasma. A 20 μg L- 1 Ge in methanol was used as internal standard for minimizing non-spectral interference, such as short-term variations due to injection. The mathematical treatment of the signal based on Fast Fourier Transform smoothing algorithm was employed to improve the precision. The concentrations of V as V-porphyrins were between 2.7 and 11 mg kg- 1 in the fractions, which were close to the total concentration of V in the porphyrin fractions of the studied crude oil.

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

    NASA Astrophysics Data System (ADS)

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

    2011-01-01

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

  20. Performance of different preconcentration columns used in sequential injection analysis and inductively coupled plasma-mass spectrometry for multielemental determination in seawater

    NASA Astrophysics Data System (ADS)

    Jiménez, María. S.; Velarte, Rosario; Castillo, Juan R.

    2002-03-01

    A simple, versatile and economical method of sequential injection analysis and inductively coupled plasma-mass spectrometry with matrix removal in two different ion-exchange resins for the determination of Al, As, Co, Cu, Mn, Mo, Ni, Pb and V is reported. The resins used, both of which contain the iminodiacetic acid functional group, were Chelex 100 and Metpac CC-1. With both resins, a matrix removal step (alkaline and alkaline-earth metals) with ammonium acetate is required before elution of the analytes with 2 M HNO 3. The procedure was validated by analyzing CASS-3 seawater reference material and good agreement was found with the certified values. Precision ( n=8) for the nine elements was in the range 0.8-4.9% for the Chelex 100 column and the recoveries ranged from 87.4 to 107.9%, except for Cu (78.7%) and Pb (74.9%), owing to the formation of hydroxides. For the Metpac CC-1 column, precision for the nine elements was in the range 1.2-7.1% and the recoveries between 91.7 and 109.3%, except for Al (127.2%), Co (118.5%) and Ni (127.5%) due to contamination problems.

  1. Variation in trace element contents among chicken, turkey, duck, goose, and pigeon eggs analyzed by inductively coupled plasma mass spectrometry (ICP-MS).

    PubMed

    Nisianakis, P; Giannenas, I; Gavriil, A; Kontopidis, G; Kyriazakis, I

    2009-04-01

    Despite substantial interest in the trace element content of eggs by poultry breeders, nutritionists, and environmental scientists, available data about trace elements levels in eggs are scarce. Trace element contents in yolk and albumen of chicken, turkey, duck, goose, and pigeon eggs were analyzed to establish a baseline dataset and assess differences among trace element content in avian species. We measured the selenium (Se), zinc (Zn), manganese (Mn), cobalt (Co), copper (Cu), molybdenum (Mo), vanadium (V), chromium (Cr), nickel (Ni), arsenic (As), cadmium (Cd), and thallium (Tl) contents in both yolk and albumen by inductively coupled plasma mass spectrometry. One hundred twenty eggs deriving from 24 birds of each species, reared in the same poultry farm in northern Greece, were used; bird feed was common and based on cereals and legumes and contained no added vitamins or microminerals. Trace element contents in yolks were far higher than those in albumen, except for V and Ni. In yolks, the highest content for Se, Mo, and Tl were in pigeon eggs, for Zn, Mn, Cu, and Cr in turkey eggs, and for Co and Ni in goose eggs. In albumen, Se was highest in duck eggs, while Zn, Mn, and Co in pigeon ones. It is concluded that there is a substantial, up to threefold, variation for trace element contents in eggs among different domestic avian species offered the same feed.

  2. Method validation for determination of metals in Vitis labrusca L. grapevine leaf extracts by inductively coupled plasma mass spectrometry (ICP-MS).

    PubMed

    Bokowski, Liane V V; Sobrinho, Roberto B; Armijo, Cristián J V; Dani, Caroline; Henriques, João A P; Funchal, Cláudia

    2016-01-01

    Vitis labrusca L. is the main species used for wine and juice production in Brazil. The grapevine leaves can be used both as functional foods and as cheapest sources for the extraction of phenolic compounds. Besides the antioxidant activity, grapevine leaves exhibited significant anti-inflammatory activity. Therefore, the aim of this study was to develop and validate an analytical methodology to determine the metals selenium (96Se), chromium (53Cr), nickel (62Ni), cadmium (111Cd) and lead (206Pb) in 30 samples of grapevine leaf extracts (Vitis labrusca, Bordo cultivar) using inductively coupled plasma mass spectrometry (ICP-MS). To obtain the grapevine leaf extracts the samples were milled, weighed and digested in microwave oven with nitric acid. The method showed linearity, precision, accuracy and limits of quantification and detection acceptable for INMETRO protocol validation of analytical methods. Therefore, the method using ICP-MS was developed and validated to determine metals concentrations in grapevine leaves of Vitis labrusca L. and the proposed method could be applied in routine analytical laboratory.

  3. [Study on the method of nanometer-size zirconium dioxide enrichment separation and inductively coupled plasma mass spectrometry determination of trace barium(II) in water].

    PubMed

    Du, Ying-Qiu; Yin, Yi-Dong; Fan, Nai-Ying; Chen, Peng-Gang; Zhang, Xiao-Bo; Ren, Hong-Bo; Chen, Guo-You; Qu, Qiu-Yao; Sun, Zhi-Bo; Chen, Yue-Xin

    2012-11-01

    Monoclinic fusiform zirconium dioxide (ZrO2) nanoparticles were synthesized by hydrothermal method, a method was established based on monoclinic fusiform nanometer-sized ZrO2 enrichment separation, and trace barium in water was determined by inductively coupled plasma mass spectrometry (ICP-MS). The detection limit for Ba(II) was 0.007 ng x mL(-1), and the relative standard deviation was 0.13% (n = 11). The optimal enrichment separation conditions of nanometer-sized ZrO2 for Ba(II) were studied in detail, it was found that the percentage of adsorbed Ba(II) was more than 99% under pH 10.0 and 2 mL 0.5 mol x L(-1) HCl was sufficient for elution of Ba(II) by more than 98%. The static adsorption capacity of ZrO2 to Ba(II) was 196.6 microg x g(-1) and enrichment factor was 250. Properties of nanometer-sized ZrO2 were discussed through regeneration experiment and effects of co-existing ions and contrast experiment to ordinary ZrO2, adsorption properties of nanometer-sized ZrO2 were applied to real samples in the analysis of Ba(II) and the determination was carried out by ICP-MS with satisfactory results.

  4. Direct trace-elemental analysis of urine samples by laser ablation-inductively coupled plasma mass spectrometry after sample deposition on clinical filter papers.

    PubMed

    Aramendía, Maite; Rello, Luis; Vanhaecke, Frank; Resano, Martín

    2012-10-16

    Collection of biological fluids on clinical filter papers shows important advantages from a logistic point of view, although analysis of these specimens is far from straightforward. Concerning urine analysis, and particularly when direct trace elemental analysis by laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) is aimed at, several problems arise, such as lack of sensitivity or different distribution of the analytes on the filter paper, rendering obtaining reliable quantitative results quite difficult. In this paper, a novel approach for urine collection is proposed, which circumvents many of these problems. This methodology consists on the use of precut filter paper discs where large amounts of sample can be retained upon a single deposition. This provides higher amounts of the target analytes and, thus, sufficient sensitivity, and allows addition of an adequate internal standard at the clinical lab prior to analysis, therefore making it suitable for a strategy based on unsupervised sample collection and ulterior analysis at referral centers. On the basis of this sampling methodology, an analytical method was developed for the direct determination of several elements in urine (Be, Bi, Cd, Co, Cu, Ni, Sb, Sn, Tl, Pb, and V) at the low μg L(-1) level by means of LA-ICPMS. The method developed provides good results in terms of accuracy and LODs (≤1 μg L(-1) for most of the analytes tested), with a precision in the range of 15%, fit-for-purpose for clinical control analysis.

  5. Asymmetric flow field-flow fractionation coupled to inductively coupled plasma mass spectrometry for the quantification of quantum dots bioconjugation efficiency.

    PubMed

    Menéndez-Miranda, Mario; Encinar, Jorge Ruiz; Costa-Fernández, José M; Sanz-Medel, Alfredo

    2015-11-27

    Hyphenation of asymmetric flow field-flow fractionation (AF4) to an on-line elemental detection (inductively coupled plasma-mass spectrometry, ICP-MS) is proposed as a powerful diagnostic tool for quantum dots bioconjugation studies. In particular, conjugation effectiveness between a "model" monoclonal IgG antibody (Ab) and CdSe/ZnS core-shell Quantum Dots (QDs), surface-coated with an amphiphilic polymer, has been monitored here by such hybrid AF4-ICP-MS technique. Experimental conditions have been optimized searching for a proper separation between the sought bioconjugates from the eventual free reagents excesses employed during the bioconjugation (QDs and antibodies). Composition and pH of the carrier have been found to be critical parameters to ensure an efficient separation while ensuring high species recovery from the AF4 channel. An ICP-MS equipped with a triple quadropole was selected as elemental detector to enable sensitive and reliable simultaneous quantification of the elemental constituents, including sulfur, of the nanoparticulated species and the antibody. The hyphenated technique used provided nanoparticle size-based separation, elemental detection, and composition analysis capabilities that turned out to be instrumental in order to investigate in depth the Ab-QDs bioconjugation process. Moreover, the analytical strategy here proposed allowed us not only to clearly identify the bioconjugation reaction products but also to quantify nanoparticle:antibodies bioconjugation efficiency. This is a key issue in future development of analytical and bioanalytical photoluminescent QDs applications.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  7. Quantification of trace elements by sector field inductively coupled plasma mass spectrometry in urine, serum, blood and cerebrospinal fluid of patients with Parkinson's disease

    NASA Astrophysics Data System (ADS)

    Bocca, B.; Alimonti, A.; Petrucci, F.; Violante, N.; Sancesario, G.; Forte, G.; Senofonte, O.

    2004-04-01

    To assess whether levels of trace metals and oxidative species are involved in Parkinson's disease (PD), Al, Be, Cd, Co, Cr, Hg, Mn, Ni, Pb and V were measured in urine, serum, blood and cerebrospinal fluid (CSF) and serum peroxides and antioxidant capacity were determined in 26 patients with PD and 13 control subjects. The quantification of metals was based on the 1+4 water dilution of CSF, serum and urine, the acid-assisted microwave digestion under atmospheric pressure of blood and final determination by sector field inductively coupled plasma mass spectrometry (SF-ICP-MS). Results indicated a significant increase of Pb and V concentrations in blood and urine ( P≤0.03, in both cases) related to the disease. Parkinson disease also seemed to be closely associated ( P≤0.003) with a reduction in levels of Al, Cd, Hg and Pb in serum and of Cd, Co, Cr, Hg, Pb in CSF. As regards Mn, a lower mean concentration was found in the CSF and whole blood of PD patients than in control group, although this trend was not statistically significant. Levels of peroxides were also increased ( P≤0.001), while antioxidant capacity was lower ( P≤0.002) in PD patients than in controls.

  8. Pharmacokinetics and tissue distribution of novel platinum containing anticancer agent BP-C1 studied in rabbits using sector field inductively coupled plasma mass spectrometry.

    PubMed

    Navolotskii, Denis V; Ivanenko, Natalya B; Solovyev, Nikolay D; Fedoros, Elena I; Panchenko, Andrey V

    2015-09-01

    A method of platinum quantification in whole blood samples after microwave digestion using sector field inductively coupled plasma mass spectrometry has been developed. The following analytical figures of merit have been established: limit of detection 1.1 µg/L for blood samples, dynamic range 3.6-200 µg/L, intra-day precision (relative standard deviation, n = 9) did not exceed 5%. Spiked samples were analyzed for method validation. The method was used for pharmacokinetics studies of a novel anti-cancer drug BP-С1, a complex of cis-configured platinum and benzene-poly-carboxylic acids. Main pharmacokinetic parameters (area under curve, maximum concentration, clearance, half-life times for α- and β-phase) were estimated for two dosage forms of BP-C1 0.05 and 0.125 mass %. Pharmacokinetic curves were assessed for single and course administration. Studies were performed using rabbits (n = 6) as a model. BP-C1 was injected intramuscularly. The study established dose proportionality of the tested dosage forms and suggested clinical dosing schedule: 5 days of injections followed by 2 days' break. Platinum tissue distribution was studied in tissue samples collected 20 days after the last injection. Predominant platinum accumulation was observed in kidneys, liver, and muscles near injection site. 'Slow' phase of platinum excretion kinetics may be related to the muscles at the injection site.

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

    PubMed

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

    2013-12-01

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

  10. Survey of inorganic arsenic in marine animals and marine certified reference materials by anion exchange high-performance liquid chromatography-inductively coupled plasma mass spectrometry.

    PubMed

    Sloth, Jens J; Larsen, Erik H; Julshamn, Kåre

    2005-07-27

    A method for the determination of inorganic arsenic in seafood samples using high-performance liquid chromatography-inductively coupled plasma mass spectrometry is described. The principle of the method relied on microwave-assisted alkaline dissolution of the sample, which at the same time oxidized arsenite [As(III)] to arsenate [As(V)], whereby inorganic arsenic could be determined as the single species As(V). Anion exchange chromatography using isocratic elution with aqueous ammonium carbonate as the mobile phase was used for the separation of As(V) from other coextracted organoarsenic compounds, including arsenobetaine. The stability of organoarsenic compounds during the sample pretreatment was investigated, and no degradation/conversion to inorganic arsenic was detected. The method was employed for the determination of inorganic arsenic in a variety of seafood samples including fish, crustaceans, bivalves, and marine mammals as well as a range of marine certified reference materials, and the results were compared to values published in the literature. For fish and marine mammals, the results were in most cases below the limit of detection. For other sample types, inorganic arsenic concentrations up to 0.060 mg kg(-)(1) were found. In all samples, the inorganic arsenic content constituted less than 1% of the total arsenic content.

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

    PubMed

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

    2014-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  13. Determination of As, Hg and Pb in herbs using slurry sampling flow injection chemical vapor generation inductively coupled plasma mass spectrometry.

    PubMed

    Tai, Chia-Yi; Jiang, Shiuh-Jen; Sahayam, A C

    2016-02-01

    Analysis of herbs for As, Hg and Pb has been carried out using slurry sampling inductively coupled plasma mass spectrometry (ICP-MS) with flow injection vapor generation. Slurry containing 0.5% m/v herbal powder, 0.1% m/v citric acid and 2% v/v HCl was injected into the VG-ICP-MS system for the determination of As, Hg and Pb that obviate dissolution and mineralization. Standard addition and isotope dilution methods were used for quantifications in selected herbal powders. This method has been validated by the determination of As, Hg and Pb in NIST standard reference materials SRM 1547 Peach Leaves and SRM 1573a Tomato Leaves. The As, Hg and Pb analysis results of the reference materials agreed with the certified values. The precision obtained by the reported procedure was better than 7% for all determinations. The detection limit estimated from standard addition curve was 0.008, 0.003, and 0.007 ng mL(-1) for As, Hg and Pb, respectively.

  14. The development of iodine based impinger solutions for the efficient capture of Hg0 using direct injection nebulization-inductively coupled plasma mass spectrometry analysis.

    PubMed

    Hedrick, E; Lee, T G; Biswas, P; Zhuang, Y

    2001-09-15

    Inductively coupled plasma mass spectrometry (ICP/MS) with direct injection nebulization (DIN) was used to evaluate novel impinger solution compositions capable of capturing elemental mercury (Hg0) in EPA Method 5 type sampling. An iodine based impinger solution proved to be very efficient for Hg0 capture and was amenable to direct analysis by DIN-ICP/MS. Hg0 capture efficiency using aqueous iodine (I3-) was comparable to Hg0 capture using acidified potassium permanganate impinger solutions which were analyzed by cold vapor atomic absorption spectrometry (CVAAS), with greater than 98% capture of Hg0 in the first oxidizing impinger. Using DIN-ICP/MS, it was demonstrated for the first time that iodine can be generated just prior to impinger sampling for efficiently oxidizing Hg0 and retaining it in solution as HgI4(2-). Due to the increased interest in Hg speciation from combustion sources and the potential for using DIN-ICP/MS for multiple metals analyses, an impinger sampling train for gaseous Hg speciation and multiple metals analyses using DIN-ICP/MS analyses is presented. The unique feature of such a sampling train is that each impinger solution in the series is amenable to direct analysis by DIN-ICP/MS. A bituminous coal was combusted in a bench scale coal system, and gaseous Hg species (oxidized and elemental) were determined using the proposed impinger train. The DIN-ICP/MS instrumental detection limit was 0.003 ppb, and MDLs ranged from 0.007 to 0.116 microg/L (ppb) in a variety of impinger solutions used for Hg capture.

  15. Analytical developments for the determination of monomethylmercury complexes with low molecular mass thiols by reverse phase liquid chromatography hyphenated to inductively coupled plasma mass spectrometry.

    PubMed

    Bouchet, Sylvain; Björn, Erik

    2014-04-25

    The behavior of monomethylmercury (MMHg) is markedly influenced by its distribution among complexes with low molecular mass (LMM) thiols but analytical methodologies dedicated to measure such complexes are very scarce up to date. In this work, we selected 15 LMM thiols often encountered in living organisms and/or in the environment and evaluated the separation of