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Sample records for ablation icp-ms u-pb

  1. Simultaneous in situ determination of U-Pb and Sm-Nd isotopes in monazite by laser ablation ICP-MS

    NASA Astrophysics Data System (ADS)

    Goudie, Dylan J.; Fisher, Christopher M.; Hanchar, John M.; Crowley, James L.; Ayers, John C.

    2014-06-01

    are presented for in situ simultaneous determination of U-Pb and Sm-Nd isotopes in monazite using the Laser Ablation Split-Stream (LASS) method. This method uses a laser ablation system coupled to a magnetic-sector inductively coupled plasma mass spectrometer (HR) (ICP-MS) for measuring U-Pb isotopes and a multicollector (MC) ICP-MS for measuring Sm-Nd isotopes. Ablated material is split using a Y-connector and transported simultaneously to both mass spectrometers. In addition to Sm and Nd isotopes, the MC-ICP-MS is configured to also acquire Ce, Nd, Sm, Eu, and Gd elemental abundances. This approach provides age, tracer isotope, and trace element data in the same ablation volume, reducing sampling problems associated with fine-scale zoning in accessory minerals and minimizing the material needed for ablation. Precision and accuracy of the U-Pb method (and the precision of the Sm-Nd method) is demonstrated with results from well-characterized monazite reference materials. The LASS results agree within uncertainty with the isotope dilution thermal ionization mass spectrometry (ID-TIMS) U-Pb dates. The accuracy of the Sm-Nd method is assessed by comparing the LA-MC-ICP-MS results with ID-TIMS determinations on a well-characterized, in-house monazite reference material. The LASS method is then applied to monazite from the Birch Creek Pluton in the White Mountains of California as a case study to illustrate the utility of this method for solving geologic problems. The U-Pb ages and Sm-Nd isotopic data from the LASS method support the conclusions drawn from previous results that monazite can record timing and information about the source region(s) of hydrothermal fluids.

  2. U-Pb Detrital Zircon Ages From the Internal Hellenides Using LA-SF-ICP-MS

    NASA Astrophysics Data System (ADS)

    Frei, D.; Meinhold, G.

    2008-12-01

    Zircon is a common accessory phase in clastic sedimentary rocks as well as one of the most stable minerals in sedimentary environments. Investigating the age spectra of detrital zircons is important for sedimentary provenance analysis to glean information regarding ancient source areas and major magmatic events, crucial for plate-tectonic and palaeogeographic reconstructions. Furthermore, in the absence of fossil and other stratigraphic data, the youngest zircon grain in a sedimentary rock can indicate a maximum limit for the age of deposition. Laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) is a rapid, comparably inexpensive and sufficiently precise technique for in-situ Pb-Pb and U-Pb age determinations of igneous, metamorphic and detrital zircons. In this study, we applied a simple method for in-situ U-Pb age determinations of zircons using a ThermoFinnigan Element2 magnetic sectorfield ICP-MS coupled to a frequency quintupled Nd-YAG (213 nm) laser ablation system. This method takes advantage of the very high sensitivity of the magnetic sectorfied ICP-MS and allows U-Pb age dating of zircons with significantly better spatial resolution (i.e. spot diameters of 30 microns and below and a depth resolution of 15 to 20 ìm) compared to quadrupole ICP-MS based methods. For this study, samples were collected from the Serbo- Macedonian Massif and the Vardar Zone of northern Greece. Both areas belong to the Internal Hellenides. There, the relationships between different pre-Alpine crustal fragments are now masked by younger (Mesozoic to Cenozoic) complex structural and metamorphic events. This, together with the scarcity of biostratigraphic, geochronological and palaeomagnetic data, has given rise to equivocal palaeotectonic models and interpretations. Detrital zircon geochronology is used here to constrain terrane accretion processes and the provenance of crustal sources for sediments during Palaeozoic and Mesozoic times. The age and origin of

  3. Common-Lead Corrected U-Pb Age Dating of Perovskite by LA-SF-ICP-MS

    NASA Astrophysics Data System (ADS)

    Frei, D.

    2014-12-01

    Perovskite is a very useful mineral for dating the age of emplacement of kimberlites and associated rocks. Conventionally, U-Pb dating of perovskite is achieved using isotope dilution (ID-TIMS) or ion-probe (SHRIMP) techniques, which are time- and cost-intensive. The potential of the rapid and inexpensive laser ablation ICP-MS technique for U-Pb dating of perovskite has been demonstrated recently. We investigated the benefits of single collector magnetic sectorfield ICP-MS (SF-ICP-MS) instruments for U-Pb dating of perovskite by laser ablation. To this end perovskites from two kimberlites from Garnet Lake, W Greenland, and Pyramidefjeld, SW Greenland, have been separated. Multigrain aliquots of both perovskite separates were U-Pb dated by ID-TIMS, yielding emplacement ages of 568 ±11 Ma for the Garnet Lake kimberlite and 151 ±2 Ma for the Pyramidefjeld kimberlite. Subsequently both samples have been dated in-situ by laser ablation employing a ThermoFinnigan Element2 SF-ICP-MS coupled to a NewWave UP 213 laser system. A common lead correction was applied based on the measured 204Pb intensity (after correction for the measured 204(Pb+Hg) gas blank). Perovskite from the Ice River Complex, British Columbia, was used as a secondary standard for quality control purposes. Multiple in-situ measurements of the Ice River perovskite in two different analytical sessions yielded concordia ages of 359 ±3 Ma and 357 ±3 Ma, in excellent agreement with the age of 356 Ma determined by ID-TIMS (Heaman, pers. comm.). Nineteen in-situ analyses of perovskite grains extracted from the Garnet Lake kimberlite yielded a concordia age of 566 ±5 Ma, also in excellent agreement with the age obtained by ID-TIMS. Because of the very low Pb contents in perovskites from the Pyramidefjeld (around 1 ppm) and the associated large uncertainties of the common lead correction, no concordia age could be obtained. However, the in-situ laser ablation analysis yielded a common lead corrected weighted

  4. Developing a Correction to Remove Systematic Bias in U-Pb LA-ICP-MS Zircon Ages Related to Zircon "Matrix Effects"

    NASA Astrophysics Data System (ADS)

    Matthews, W. A.; Angelo, T. V.; Guest, B.

    2014-12-01

    For more than a decade the occurrence of systematic discrepancies between the U-Pb ages of zircons determined by LA-ICP-MS and ID-TIMS has been acknowledged. Trace element concentrations, crystallographic orientation and damage to the crystal lattice by radioactive decay have all been cited as possible causes for the discrepancy termed the "matrix effect". Recent studies have concluded that differences in Laser Induced Elemental Fractionation (LIEF) between zircon reference materials results from variations in the ablation rate between the primary reference, which is used to build a model for LIEF during data reduction, and the unknowns. These variations are likely related to physical differences in the crystal lattice caused by alpha particle ejection. We tested this hypothesis by measuring the ablation rate for ~200 individual ablation pits in a variety of reference materials using an optical profilometer. Our data demonstrate a clear relationship between delta age (the difference between the age calculated by LA-ICP-MS and the accepted ID-TIMS age, expressed as a percentage) and ablation rate. The relationship between calculated alpha dosage for each ablation and delta age is less clear. This suggests that the zircon's thermal history may play an important role in controlling ablation rate through annealing of crystal lattice defects. However, alpha dosage is readily quantifiable during routine zircon U-Pb analyses and therefore its relationship to delta age may provide a useful first order correction to remove systematic biases from U-Pb ages. Raman spectroscopy could provide a more robust measure of radiation damage in the zircon lattice and could help to refine our understanding of the processes involved.

  5. Characterizing Carbonates from the Sheep Pass Formation, Nevada Using Laser Ablation ICP-MS

    NASA Astrophysics Data System (ADS)

    Piccione, G.; Rasbury, T.; Davis, D. M.; Druschke, P.; Hanson, A. D.; Parrish, R. R.; Austin-Giddings, W.

    2014-12-01

    Laser ablation plasma mass spectrometry allows for rapid high spatial resolution sampling, which is favorable for geochemically variable samples such as carbonates. This method also allows characterization of samples through the evaluation of elements, element ratios, and isotope ratios. Pairing LA ICP-MS with paragenetic studies provides the ability to geochemically characterize physically distinguishable fluid events that formed new phases. This is particularly useful for analysis of vein filling minerals, which can then be attributed to a tectonic or magmatic event. Coupling elemental analyses with U-Pb dating allows us to not only date the timing of mineralization and its associated tectonic activity, but also to better characterize the fluids in order to understand where they came from and what they may have interacted with. A suite of carbonates from the basal member of the Sheep Pass Formation in east-central Nevada was analyzed using LA ICP-MS, yielding U-Pb ages that are in agreement with both the ages found using ID TIMS and the known age of that member. An age was also attained for fluorite from a vein that cuts the dated Sheep Pass member. This age is distinctly younger than the lacustrine carbonates and is consistent with evidence that the major bounding faults of this basin have experienced multiple phases of movement.

  6. U-Pb Dating of CA/non-CA Treated Zircons Obtained by LA-ICP-MS and CA-TIMS Techniques: Impact for their Geological Interpretation

    NASA Astrophysics Data System (ADS)

    Von Quadt, A.; Gallhofer, D.; Guillong, M.; Peytcheva, I.

    2014-12-01

    Chemical Abrasion Isotope-Dilution Thermal Ionization Mass Spectrometry (CA-ID-TIMS) is known as a high precision technique for resolving lead loss and improving the interpretation of U-Pb zircon age data. We argue that combining CA with the widely applied Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) improves the precision and accuracy of zircon dates, while removing the substantial parts with lead loss, reducing data scatter, and providing meaningful geological interpretations. The samples are magmatic rocks chosen from different geological time periods (Paleozoic, Mesozoic and Cenozoic time). All zircon separates are analysed by LA-ICP-MS before and after CA, and all age data are compared with CA-ID-TIMS 206Pb/238U dates that are considered as the most accurately age. All CA-treated zircon crystals show up to 50% less data scatter compared to the non-CA treated zircon grains and thus a reduction of the calculated uncertainties is apparent. The obtained wt average LA-ICP-MS 206Pb/238U ages of the CA-treated zircon grains are up to 4-6% higher than those of the non-CA treated crystals, exceeding the analytical uncertainties of the LA-ICP-MS dating technique of 1-2%. The damaged crystal parts, caused by U-decay, with lead loss are removed, so that we can exclude younging from the possible geological scenarios. CA-LA-ICP-MS age data are in good agreement with the CA-ID-TIMS dates and suggest advantages of using CA-LA-ICP-MS in order to define accurate ages. The use of the CA technique for very young zircons (~0.2 Ma, Kos rhyolitic tuff, Greece) seems optional; as the obtained mean 206Pb/238U ages of non-CA and CA treated zircons coincide within the uncertainty. The negligible time to produce the lattice damage (based on alpha decay or spontaneous fission) makes lead loss less important for age dating and data interpretation of very young zircons (<1 Ma). Von Quadt, A. et al., 2014, JAAS, doi: 10.1039/c4ja00102h.

  7. A Modern Analog to the Depositional Age Problem: Zircon and Apatite Fission Track and U-Pb Age Distributions by LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Donelick, H. M.; Donelick, M. B.; Donelick, R. A.

    2012-12-01

    Sand from three river systems in North Idaho (Snake River near Lewiston, Clearwater River near Lewiston and the Salmon River near White Bird) and two regional ash fall events (Mt. Mazama and Mt. St. Helens) were collected for zircon U-Pb detrital age analysis. Up to 120 grains of zircon per sample were ablated using a Resonetics M-50 193 nm ArF Excimer laser ablation (LA) system and the Pb, Th, and U isotopic signals were quantified using an Agilent 7700x quadrupole inductively coupled plasma-mass spectrometer (ICP-MS). Isotopic signals for major, minor, and trace elements, including all REEs, were also monitored. The youngest zircon U-Pb ages from the river samples were approximately 44 Ma; Cenozoic Idaho Batholith and Precambrian Belt Supergroup ages were well represented. Significant common Pb contamination of the Clearwater River sample (e.g., placer native Cu was observed in the sample) precluded detailed analysis of the zircon U-Pb ages but no interpretable ages <44 Ma were observed. Interestingly, not one of the river samples yielded zircon U-Pb ages near 0 Ma, despite all three catchment areas having received significant ash from Mt. St. Helens in 1980, and Mount Mazama 7,700 years ago, and no doubt other events during the Quaternary. Work currently in progress seeks to address bias against near 0 Ma ages in the catchment areas due to: a) small, local ash fall grain sizes and b) overwhelming number of older grains relative to the ash fall grains. Data from Mt. St. Helens ash from several localities near the mountain (Toutle River and Maple Flats, WA) and several far from the mountain (Spokane, WA; Princeton, ID; Kalispell, MT) and Mt. Mazama ash fall deposits near Lewiston, ID and Spokane, WA will be presented to address these possibilities. Additionally, fission track and U-Pb ages from apatites collected from these river and ash fall samples will also be shown to help constrain the problem.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  9. Mid-Paleozoic arc granitoids in SW Japan with Neoproterozoic xenocrysts from South China: New zircon U-Pb ages by LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Aoki, Kazumasa; Isozaki, Yukio; Yamamoto, Atsushi; Sakata, Shuhei; Hirata, Takafumi

    2015-01-01

    The Kurosegawa belt in SW Japan preserves fragments of Early-Middle Paleozoic granitoids traditionally called the Mitaki igneous rocks and previously dated ca. 470-435 Ma by several isotope analyses such as Rb-Sr, K-Ar and U-Pb, together with high-grade metamorphic rocks and Silurian strata, in a narrow belt. However, the timing of the oldest arc-related plutonism in Japan is constrained by laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) U-Pb ages of zircon from Mitaki granitoids in 3 areas in SW Japan; i.e. Kyushu, Shikoku, and Kii Peninsula. Weighted mean U-Pb ages of these zircons are 431.8 ± 3.9 for a granodiorite from the Mt. Mitaki area in Shikoku, 444.1 ± 5.8 Ma for a granodiorite from Kuraoka area in central Kyushu, and 444.5 ± 7.6 Ma for a quartzdiorite from the Nabaenohana area in western Kii peninsula, respectively. These ages confirm that the Mitaki igneous rocks have ca. 445-435 Ma (late Ordovician to mid-Silurian) ages. They are some of the oldest subduction-related plutonic rocks in SW Japan. Particularly noteworthy is a "tonalite" from the Nabaenohana area, which has a unique spectrum of zircon U-Pb ages with distinct 3 clusters; ca. 700-500 Ma (Neoproterozoic-Cambrian), ca. 1350-830 Ma (Meo-Neoproterozoic), and ca. 3230-1560 Ma (Paleoarchean-Mesoproterozoic). Of the 44 dated zircon grains, the youngest (possibly xenocrystic) grains are ca. 500 Ma. Older zircon grains with ages >500 Ma range up to 3230 Ma and are interpreted as inherited xenocrysts in the "tonalite". The Mitaki igneous rocks are interpreted to have been derived by melting of post-500 Ma terrigenous sedimentary rocks that yielded a unique tonalitic S-type granitoid magma. From the presence of abundant 1350-700 Ma (Meso- to Neoproterozoic) zircon grains in the "tonalite" we conclude that during the Early Paleozoic, proto-Japan was located close to the Cathaysian margin of South China.

  10. Zircon U-Th-Pb dating using LA-ICP-MS: Simultaneous U-Pb and U-Th dating on the 0.1 Ma Toya Tephra, Japan

    NASA Astrophysics Data System (ADS)

    Ito, Hisatoshi

    2014-12-01

    Simultaneous U-Pb and U-Th zircon dating using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was performed on the ~ 0.1 Ma Toya Tephra, Hokkaido, Japan. The method employs the concurrent measurement of 206Pb, 230Th, and 238U signals, which enables the determination of 238U-206Pb (U-Pb) and 238U-230Th (U-Th) ages simultaneously. The U-Pb ages revealed that the Toya Tephra contains zircons with ages that cluster at ~ 0.1 Ma (0.11 ± 0.01 Ma: error shown as 95% confidence level) and xenocrysts with ages > 2 Ma. Excluding zircons > 2 Ma, the U-Th method also gave an isochron age of ~ 0.1 Ma (108 ± 19 ka or 0.11 ± 0.02 Ma; error shown as 2σ). Therefore, both U-Pb and U-Th methods result in similar ages of ~ 0.1 Ma for the Toya Tephra, in agreement with the quartz TL age (104 ± 30 to 118 ± 30 ka) of Ganzawa and Ike (2011). It was revealed that the simultaneous U-Pb and U-Th zircon dating technique using LA-ICP-MS is easy to apply and is useful for Quaternary tephras in that it can give age information on the tephra itself and xenocrystic zircons in a quick and cost-effective manner. The double dating technique employed here has the merit that zircons yielding Quaternary U-Pb ages can be immediately cross-checked by the U-Th method. It was also revealed that the Toya Tephra magma crystallized zircons and experienced eruptions instantaneously at ~ 0.1 Ma, which is an important implication to decipher magmatic and eruptive processes for caldera-forming large volcanic systems.

  11. Lengthy Ultrahigh-Pressure Metamorphism demonstrated by laser ablation split-stream ICP-MS

    NASA Astrophysics Data System (ADS)

    Kylander-Clark, A. R.; Hacker, B. R.; Ginsburg, A. A.; Spencer, K.

    2011-12-01

    There is much disagreement about the maximum duration of ultrahigh-pressure (UHP) events. Some have argued for >20 Myr timescales based on geochronology, whereas others have countered that such conclusions are unsound because of the likelihood of inherited age components or because the long reach of thermal conduction is likely to induce melting and assimilation of the UHP terrane into the mantle. To assess these two possibilities we analyzed accessory minerals from eclogites and HP gneisses in the Western Gneiss Region of Norway using laser ablation split-stream (LASS) ICP-MS. LASS allows concurrent collection of trace, rare-earth element (REE), and U-Th-Pb data to directly link metamorphic conditions with the age of each spot analysis. Zircons from eclogite yield garnet-stable U-Pb ages (as shown by depressed HREE signatures) from as early as ~450 Ma, to as late as ~400 Ma; the bulk of these ages span 425-402 Ma. Monazites from grt-ky gneisses yield U-Pb and Th-Pb ages from 425-386 Ma and HREE, Eu*, Y and Sr contents that imply garnet growth and feldspar breakdown from 425-405 Ma, similar to the data of eclogite zircons. Monazite ages younger than 400 Ma contain elevated HREE and lower Sr contents, implying garnet breakdown and feldspar growth. The age and element data of the youngest, retrograde monazites are consistent with zircon LASS data from late-stage leucosomes, dikes, and stocks, which have U-Pb ages of 407-392 Ma and elevated HREEs. Titanite data complement the late-stage, garnet-poor zircon and monazite ages (~400-380 Ma), indicating up to 20 Myr of exhumation from the most profound depths. In summary, these LASS data force the interpretation that subduction of the Baltica craton was well underway by 425 Ma and reached its maximum depth prior to the onset of exhumation and rise to amphibolite-facies depths at ~405 Ma. Exhumation, melting, and metamorphic growth continued through at least 386 Ma.

  12. 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.

  13. Zircon U-Pb and trace element zoning characteristics in an anatectic granulite domain: Insights from LASS-ICP-MS depth profiling

    NASA Astrophysics Data System (ADS)

    Marsh, Jeffrey H.; Stockli, Daniel F.

    2015-12-01

    Understanding the geochemical characteristics of metamorphic zircon, and how they may be modified by recrystallization processes, is fundamental to defining the timescales of tectonic processes affecting continental lithosphere. We utilize laser ablation split-stream (LASS)-ICP-MS depth-profiling analysis to obtain a continuous rim-to-core record of the U-Pb ages and trace-element composition preserved within variably recrystallized zircon from different rock types within a well-studied granulite domain in the western Grenville Province, Canada. Detailed analysis of the depth-resolved signal enables definition of chemically distinct (homogeneous) internal domains and heterogeneous intervening zones that can generally be correlated with textural features observed in CL. Three age populations have been distinguished within the ~ 35 μm deep profiles that correlate well with the established timing of protolith formation, granulite-facies metamorphism, and amphibolite-facies shearing, respectively. The U-Pb isotopic system and Th/U ratios in much of the crystal interiors have undergone considerable modification, as evidenced by a linear correlation between 207Pb/206Pb age and Th/U ratio. Interior and rim domains commonly contain blurred or faded oscillatory zoning patterns, suggesting that solid-state recrystallization is at least partially responsible for the modified U-Th-Pb composition. A number of systematic trends in trace element composition are also observed between interior domains and recrystallized rims, including 1) decreased Th/U (to ~ 0.1), 2) tighter clustering of Hf concentrations, 3) decreased total REE, 4) unchanged Eu anomalies, and 5) a widened spread of HREE enrichment values (YbN/GdN). Both YbN/GdN vs. Th/U and U/Ce vs. Th plots show increasing degree of compositional differentiation from protolith zircon as a function of metamorphic reworking processes (i.e. sample type). The transition zones between interior and rim domains exhibit textural

  14. Application of laser microdissection ICP-MS for high resolution elemental mapping in mouse brain tissue: a comparative study with laser ablation ICP-MS.

    PubMed

    Sussulini, Alessandra; Becker, J Sabine

    2015-01-01

    Mapping of elements in biological tissue by laser induced mass spectrometry is a fast growing analytical methodology in life sciences. This method provides a multitude of useful information of metal, nonmetal, metalloid and isotopic distribution at major, minor and trace concentration ranges, usually with a lateral resolution of 12-160 µm. Selected applications in medical research require an improved lateral resolution of laser induced mass spectrometric technique at the low micrometre scale and below. The present work demonstrates the applicability of a recently developed analytical methodology - laser microdissection associated to inductively coupled plasma mass spectrometry (LMD ICP-MS) - to obtain elemental images of different solid biological samples at high lateral resolution. LMD ICP-MS images of mouse brain tissue samples stained with uranium and native are shown, and a direct comparison of LMD and laser ablation (LA) ICP-MS imaging methodologies, in terms of elemental quantification, is performed. PMID:25476347

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

    PubMed

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

    2014-08-01

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

  16. Optimization of the in-situ U-Pb age dating method via LA-Quadrupole-ICP-MS with applications to the timing of U-Zr-Mo mineralization in the Poços de Caldas Alkaline Complex, SE Brazil

    NASA Astrophysics Data System (ADS)

    Takenaka, Lynthener Bianca; Lana, Cristiano; Scholz, Ricardo; Nalini, Herminio Arias, Jr.; de Abreu, Adriana Tropia

    2015-10-01

    The high spatial resolution of the LA-ICP-MS systems allows rapid extraction of vital isotopic information from individual growth zones of minerals. This paper describes in detail the optimization of a relatively inexpensive LA-ICP-MS system consisting of a UV 213 Laser Ablation and a Quadrupole ICP-MS. The results of optimization take into account laser energy, beam diameter, frequency and ICP-MS gas conditions. The optimized conditions were tested for precision and accuracy on a number of well-characterized zircons, commonly used as primary and secondary quality control standards. The acquisition of the U-Pb data is carried out in automated mode (pre-set points) for up to 12 h/day with only minimal operator presence. Individual U-Pb zircon analysis lasts 80 s. The 2σ uncertainties of the standards ranged between 1.4 and 8.2%, and overall their relative deviations ranged from 0.02 to 0.87%. The results are comparable to techniques that use more complex and time-consuming approaches such as LA-MC-ICP-MS and ion-microprobe. We have applied this method to obtain ages of numerous granitoid rocks from the Southern São Francisco Craton and a well-known Archean granitoid of the Kaapvaal Craton, South Africa. We furthermore provide the first results of U-Pb age dating of U-Zr-Mo mineralization in the Poços de Caldas Alkaline Complex, SE Brazil, with a U-Pb age of 85 ± 3 Ma for zircon-bearing hydrothermal veins.

  17. Results of U-Pb LA-ICP-MS dating of detrital zircons from Ediacaran-Early Cambrian deposits of the eastern part of the Baltic monoclise

    NASA Astrophysics Data System (ADS)

    Ivleva, A. S.; Podkovyrov, V. N.; Ershova, V. B.; Anfinson, O. A.; Khudoley, A. K.; Fedorov, P. V.; Maslov, A. V.; Zdobin, D. Yu.

    2016-06-01

    Here we present the results of U-Pb LA-ICP-MS dating of detrital zircons from the Ediacaran-Early Cambrian deposits of the eastern part of the Baltic monoclise (Leningrad Region). The obtained age spectra of the detrital zircons suggest that, in the Ediacaran-Early Cambrian, the main clastic material source to the northwest of the Russian Platform was the Baltic Shield. Then in the Early Cambrian along with the Baltic Shield provenance, a clastic source from the Timanian margin of Baltica (northeast in modern coordinates) contributed to the deposits. The obtained data either somewhat set limits of the Timanian orogen formation as older than the previously suggested Middle Cambrian (about 510 Ma), based on the "absence of a Proto-Uralian-Timanian provenance signal" in the Sablino Formation rocks in the south Ladoga, or suggest another rearrangement of detritus transportation paths at the end of Stage 3 (Atdabanian).

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  19. Advances in the measurement of sulfur isotopes using laser ablation MC-ICP- MS

    NASA Astrophysics Data System (ADS)

    Ridley, W. I.; Pribil, M. J.; Koenig, A. E.; Fayek, M.; Slack, J. F.

    2008-05-01

    Although sulfur is poorly ionized in an argon plasma, there are many applications for sulfur isotope analysis using an ICP source. Studies using a desolvation system (DSN) and an aqueous source of sulfur, where the sulfur is complexed with a cation to form a sulfur salt, e.g., calcium or sodium to provide a stable delivery of sulfur through the sample introduction system indicate that precision (~ 0.3 per mil) and accuracy are maintained at sulfur concentrations as low as 1 mg/L. Based on this data, solid sampling of sulfides and sulfates can provide an adequate amount supply of sulfur to an ICP source, even allowing for the relatively poor transport efficiency of laser ablation systems. The main limitations on accuracy and precision are the initial sampling volume, principally a function of spot size and laser fluence and the decreased instrument sensitivity resulting from the pseudo- medium or high resolution mode of analysis required to eliminate polyatomic isobaric interferences. These factors, in turn, determine the minimal grain size necessary for analysis. There are also fit-for-purpose considerations. For instance, many base metal sulfide systems have large variations in sulfur isotope composition, so that precision as poor as one per mil can still provide useful information. Here, we describe the methodology used at the USGS for laser ablation analysis of sulfides and sulfates using a second generation MC-ICP-MS and demonstrate the accuracy of the method based upon a grain-by-grain comparison of laser ablation and ion microprobe sulfur isotope data. A laser ablation MC-ICP-MS study of base metal mineralization at Dry Creek deposit, east-central Alaska demonstrates that the range in sulfur isotope composition of pyrite, sphalerite and galena, based on analysis of individual grains, is almost twice that reported for any other individual VMS deposit. Analysis on the microscopic scale thus provides additional insights into the potential sources of sulfur for

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

    NASA Astrophysics Data System (ADS)

    Ridley, W. I.

    2003-04-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2005-01-01

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

  2. Temporal and Spatial Fluctuations in Ancestral Northern Cascade Arc Magmatism from New LA-ICP-MS U-Pb Zircon Dating

    NASA Astrophysics Data System (ADS)

    McCallum, I. S.; Mullen, E.; Jean-Louis, P.; Tepper, J. H.

    2015-12-01

    Mt. Baker and the adjacent Chilliwack batholith (MBC focus) in NW Washington preserve the longest magmatic record in the Cascade Arc, providing an excellent natural laboratory for examining the spatial, temporal and geochemical evolution of Cascade magmatism and links to tectonic processes. We present new U-Pb zircon LA-ICP-MS ages for 14 samples from MBC and neighboring regions of the north Cascades. The new results are up to 8 Myr different from previous K-Ar ages, illustrating the need for new age determinations in the Cascades. A maximum age of 34.74±0.24 Ma (2σ) (Post Creek stock) is consistent with 35-40 Ma ages for arc inception in the southern Cascades. The most voluminous MBC plutons cluster at 32-29 Ma, consistent with an early flare-up that also coincides with intrusion of the Index batholith farther south (2 samples at 33.26±0.19, 33.53±0.15 Ma). This flare-up is absent in the northernmost Cascades where the oldest pluton (Fall Creek stock) is 6.646±0.046 Ma, 4 Myr younger than previously cited. Earliest Cascade magmatism is progressively younger to the north of MBC, possibly tracing the northerly passage of the slab edge. MBC activity was continuous to 22.75±0.17 Ma (Whatcom Arm), marking the initiation of an 11 Myr hiatus. Magmatism resumed at 11.33±0.08 Ma (Indian Creek) and continued to the modern Mt. Baker cone, defining a pattern of southwesterly migration over ~55 km that may be attributable to slab rollback and arc rotation (e.g. Wells & McCaffrey 2013). Uniformity of the rate and direction of migration implies that rollback and rotation began at least 11 Myr ago. Post-hiatus magmas show distinct geochemical and petrologic characteristics including a major Pb isotopic shift. The 2.430±0.016 Ma Lake Ann stock contains 4.2 Ma zircon antecrysts, recording prolonged activity in that area. The 1.165±0.013 Ma Kulshan caldera ignimbrite contains ~200 Ma inherited zircons that may provide the first direct record of Wrangellian basement beneath

  3. Sediment profiles of less commonly determined elements measured by Laser Ablation ICP-MS.

    PubMed

    Dolor, Marvourneen K; Helz, George R; McDonough, William F

    2009-01-01

    Anthropogenic influences on trace element profiles in dated sediments from estuaries have been often documented, with the vast majority of studies focusing on a short list of high-abundance trace elements. Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) provides a new approach that minimizes sample preparation and contamination while yielding data on a much larger list of elements simultaneously. We present concentrations and enrichment factor profiles for 22 elements at a locality that is 50 km southeast of Baltimore, the principal industrial city on Chesapeake Bay. Samples representing deposition over almost the entire 20th century were obtained from two archived cores collected 20 years apart. The following elements exhibit profiles consistent with a strong anthropogenic influence, i.e. enrichment after 1920 followed by decline after ca.1980, possibly reflecting increased regulatory efforts: Mn, Co, Cu, Zn, Ag, Cd, In, Sn, Sb, Te, Tl, Pb and Bi. As expected, the redox-sensitive elements: Mo, Re and U have similar profiles to one another. Previously, the potentially hazardous elements, Ag, In, Sb, Te, Tl and Bi, have been measured only rarely in estuarine sediments and never in Chesapeake Bay. Our discovery that their profiles track those of well-known pollutants underscores a need to investigate their sources, transport and biogeochemical behavior. Several rarely determined trace elements, Ga, Ge and Nb, exhibit trendless profiles, as do the major elements, Ti and Fe.

  4. Laser ablation-ICP-MS depth profiling to study ancient glass surface degradation.

    PubMed

    Panighello, Serena; Van Elteren, Johannes T; Orsega, Emilio F; Moretto, Ligia M

    2015-05-01

    In general the analysis of archeological glass represents a challenge for a wide variety of objects because of the presence of physical and/or chemical damage on the surface of the artifact, also known as weathering or corrosion. To retrieve accurate bulk elemental information by laser ablation-inductively coupled plasma-mass spectrometry (ICP-MS), the original, pristine glass needs to be "reached", thereby penetrating the alteration layer which is often more than 10 μm thick. To study this alteration layer the laser was operated in the drilling mode, either with a low (1 Hz) or a high (10 Hz) pulse repetition rate for a period of 50 s yielding detailed spatial information for ca. 20 elements over a shallow depth (ca. 5 μm) or less-detailed spatial information for 50-60 elements over a greater depth (ca. 50 μm). Quantitative elemental depth profiles (in wt%) were obtained with the so-called sum normalization calibration protocol, based on summation of the elements as their oxides to 100 wt%. We were able to associate the increase of SiO2 (in wt%) in the alteration layer to the volumetric mass density change in the glass as a result of depletion of Na2O and K2O. Also the interaction of the number of laser shots with the alteration layer is shown experimentally via depth measurements using profilometry. Chemical and physical changes in four ancient glass artifacts, directly and indirectly measureable by laser drilling, were studied as a function of internal and external factors such as age, composition, and exposure conditions.

  5. High Spatial Resolution Analysis of Carbonates by In Situ Excimer Laser Ablation MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Shuttleworth, S.; Lloyd, N.; Douthitt, C.

    2012-12-01

    Speleothems are important climate archives. The time resolution of the paleochlimate proxies depends on the growth rates and the precision limitation of the analytical instrumentation [1]. As a consequence, for speleothems, better analytical precision combined with better spatial resolution will always be the goal, driven by a need to probe the timing and duration of climate events [1]. The Thermo Scientific NEPTUNE Plus with Jet Interface option offers unparalleled MC-ICP-MS sensitivity for heavy elements. An ion yield of >3 % has previously been reported for uranium solutions introduced by desolvating nebulizer[2]. For laser ablation Hf, the Jet Interface with N2 addition significantly improved sensitivity, which allowed precise and accurate 176Hf/177Hf ratios to be calculated using a spot size of just 25 μm diameter [3]. A Thermo Scientific NEPTUNE Plus with Jet Interface option was coupled with a Photon Machines excimer laser ablation system. This system features a short pulse width (4ns) 193 nm excimer laser and the HELEX 2 volume sample cell. The 193nm wavelength has been shown to reduce the particle size distribution of the aerosol produced by the laser ablation process [4] and this in turn has been shown to help minimize the effects of fractionation by ensuring that particles are in a size range so as to avoid incomplete vaporization and ionization in the plasma [5]. In this work we investigate U-Th dating of carbonates. Accurate LA U-Th isotope measurements on carbonates with U concentrations smaller than 1 μg/g are difficult due to small ion beams [1]. Hoffman et. al. [1] noted individual LA U-Th ratio precisions of about 2% (2 sigma) on a 134 ka sample with 134 μg/g U concentration. In this work we apply a combination of the high sampling efficiency two volume cell plus mixed gas plasmas to further enhance the capability. [1] Hoffman, D.L., et al. (2009). Chemical Geology. 259 253-261 [2] Bouman, C., et al. (2009). Geochim. Cosmochim. Acta. 73

  6. Speciation of iodine-containing proteins in Nori seaweed by gel electrophoresis laser ablation ICP-MS.

    PubMed

    Romarís-Hortas, V; Bianga, J; Moreda-Piñeiro, A; Bermejo-Barrera, P; Szpunar, J

    2014-09-01

    An analytical approach providing an insight into speciation of iodine in water insoluble fraction of edible seaweed (Nori) was developed. The seaweed, harvested in the Galician coast (Northwestern Spain), contained 67.7±1.3 μg g(-1) iodine of which 25% was water soluble and could be identifies as iodide. Extraction conditions of water insoluble residue using urea, NaOH, SDS and Triton X-100 were investigated. The protein pellets obtained in optimized conditions (after precipitation of urea extracts with acetone), were digested with trypsin and protease XIV. Size exclusion chromatography-ICP-MS of both enzymatic digests demonstrated the occurrence of iodoaminoacids putatively present in proteins. Intact proteins could be separated by gel electrophoresis after an additional extraction of the protein extract with phenol. Sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS PAGE) with laser ablation ICP-MS detection of (127)I indicated the presence of iodine in protein bands corresponding to molecular masses of 110 kDa, 40 kDa, 27 kDa, 20 kDa and 10 kDa. 2D IEF-SDS PAGE with laser ablation ICP-MS (127)I imaging allowed the detection of 5 iodine containing protein spots in the alkaline pI range.

  7. Determination of trace elements in zeolites by laser ablation ICP-MS.

    PubMed

    Pickhardt, C; Brenner, I B; Becker, J S; Dietze, H J

    2000-09-01

    Laser ablation inductively coupled plasma mass spectrometry using a quadrupole-based mass spectrometer (LA-ICP-QMS) was applied for the analysis of powdered zeolites (microporous aluminosilicates) used for clean-up procedures. For the quantitative determination of trace element concentrations three geological reference materials, granite NIM-G, lujavrite NIM-L and syenite NIM-S, from the National Institute for Metallurgy (South Africa) with a matrix composition corresponding to the zeolites were employed. Both the zeolites and reference materials were fused with a lithium borate mixture to increase the homogeneity and to eliminate mineralogical effects. In order to compare two different approaches for the quantification of analytical results in LA-ICP-MS relative sensitivity coefficients (RSCs) of chemical elements and calibration curves were measured using the geostandards. The experimentally obtained RSCs are in the range of 0.2-6 for all elements of interest. Calibration curves for trace elements were measured without and with Li or Ti as internal standard element. With a few exceptions the regression coefficients of the calibration curves are better than 0.993 with internal standardization. NIM-G granite reference material was employed to evaluate the accuracy of the technique. Therefore, the measured concentrations were corrected with RSCs which were determined using lujavrite reference material NIM-L. This quantification method provided analytical results with deviations of 1-11% from the recommended and proposed values in granite reference material NIM-G, except for Co, Cs, La and Tb. The relative standard deviation (RSD) of the determination of the trace element concentration (n = 5) is about 1% to 6% using Ti as internal standard element. Detection limits of LA-ICP-QMS in the lower microg/g range (from 0.03 microg/g for Lu, Ta and Th to 7.3 microg/g for Cu, with the exception of La) have been achieved for all elements of interest. Under the laser ablation

  8. Determination of trace elements in zeolites by laser ablation ICP-MS.

    PubMed

    Pickhardt, C; Brenner, I B; Becker, J S; Dietze, H J

    2000-09-01

    Laser ablation inductively coupled plasma mass spectrometry using a quadrupole-based mass spectrometer (LA-ICP-QMS) was applied for the analysis of powdered zeolites (microporous aluminosilicates) used for clean-up procedures. For the quantitative determination of trace element concentrations three geological reference materials, granite NIM-G, lujavrite NIM-L and syenite NIM-S, from the National Institute for Metallurgy (South Africa) with a matrix composition corresponding to the zeolites were employed. Both the zeolites and reference materials were fused with a lithium borate mixture to increase the homogeneity and to eliminate mineralogical effects. In order to compare two different approaches for the quantification of analytical results in LA-ICP-MS relative sensitivity coefficients (RSCs) of chemical elements and calibration curves were measured using the geostandards. The experimentally obtained RSCs are in the range of 0.2-6 for all elements of interest. Calibration curves for trace elements were measured without and with Li or Ti as internal standard element. With a few exceptions the regression coefficients of the calibration curves are better than 0.993 with internal standardization. NIM-G granite reference material was employed to evaluate the accuracy of the technique. Therefore, the measured concentrations were corrected with RSCs which were determined using lujavrite reference material NIM-L. This quantification method provided analytical results with deviations of 1-11% from the recommended and proposed values in granite reference material NIM-G, except for Co, Cs, La and Tb. The relative standard deviation (RSD) of the determination of the trace element concentration (n = 5) is about 1% to 6% using Ti as internal standard element. Detection limits of LA-ICP-QMS in the lower microg/g range (from 0.03 microg/g for Lu, Ta and Th to 7.3 microg/g for Cu, with the exception of La) have been achieved for all elements of interest. Under the laser ablation

  9. Reply to Comment on "Zircon U-Th-Pb dating using LA-ICP-MS: Simultaneous U-Pb and U-Th dating on the 0.1 Ma Toya Tephra, Japan"

    NASA Astrophysics Data System (ADS)

    Ito, Hisatoshi

    2015-04-01

    Guillong et al. (2015) mentioned that corrections for abundance sensitivity for 232Th and molecular zirconium sesquioxide ions (Zr2O3+) are critical for reliable determination of 230Th abundances in zircon for LA-ICP-MS analyses. There is no denying that more rigorous treatments are necessary to obtain more reliable ages than those in Ito (2014). However, as shown in Fig. 2 in Guillong et al. (2015), the uncorrected (230Th)/(238U) for reference zircons except for Mud Tank are only 5-20% higher than unity. Since U abundance of Toya Tephra zircons that have U-Pb ages < 1 Ma is in-between that of FCT and Plesovice, the overestimation of 230Th by both abundance sensitivity and molecular interferences is expected to be 5-20% for the Toya Tephra. Moreover Ito (2014) obtained U-Th ages of the Toya Tephra by comparison with Fish Canyon Tuff (FCT) data. Because both the FCT and the Toya Tephra have similar trends of overestimation of 230Th, the effect of overestimation of 230Th to cause overestimation of U-Th age should be cancelled out or negligible. Therefore the pivotal conclusion in Ito (2014) that simultaneous U-Pb and U-Th dating using LA-ICP-MS is possible and useful for Quaternary zircons holds true.

  10. Silurian U-Pb zircon age (LA-ICP-MS) of granitoids from the Zelenodol Cu-porphyry deposit, Southern Urals

    NASA Astrophysics Data System (ADS)

    Grabezhev, A. I.; Ronkin, Yu. L.; Puchkov, V. N.; Shardakova, G. Yu.; Azovskova, O. B.; Gerdes, A.

    2016-01-01

    The Zelenodol porphyry Cu-(Au, Mo) deposit located about 65 km SSW of the city of Chelyabinsk is confined to the western part of the West Uralian Volcanogenic Megazone. The concordant U-Pb age of zircons from ore-bearing island-arc diorite porphyryis 418.3 Â ± 2.9 Ma.

  11. 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.

  12. 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.

  13. "Sands of Pangea"-analysing the supercontinent formation and the Mesozoic sedimentary record using LA ICP MS U Pb zircon dating on samples from Germany-

    NASA Astrophysics Data System (ADS)

    Hofmann, Mandy; Linnemann, Ulf; Gerdes, Axel; Voigt, Thomas

    2013-04-01

    The Elbe Zone at the northern Bohemian Massif (part of the Central European Variscides, Saxony, Germany) contains important structures and outcrops that help to understand the final pulse of the Variscan Orogeny in Europe leading to the formation of supercontinent Pangea. We will present zircon U-Pb data from that area that allow the timing of the final stage of these movements and of related plutonic, volcano-sedimentary and tectonic processes. In addition, we will show U-Pb detrital zircon ages of sandstones from the Triassic, Jurassic and Cretatceous of Germany to draw conclusions about the sedimentary record and the source areas (provenance analyses) of these "sands of Pangea". We have analysed detrital zircon grains from the Buntsandstein (Lower Triassic) and the Keuper (Upper Triassic) regarding their U-Pb ages. These analyses indicate different zircon ages with a main peak at ca. 250 Ma to ca. 700 Ma. Distinct zircon grains of Meso- and Paleoproterozoic ages were found. In addition to the Triassic samples we analysed detrital zircon grains from the Middle Jurassic (Dogger) and the Cretaceous. The Cretaceous samples show similar ages as the Triassic ones: the main peak of zircon ages lies between ca. 240 Ma and 700 Ma. Also, there are a few isolated zircon grains with Meso- to Paleoproterozoic ages. A real change shows the Jurassic Sandstone, as the zircons of this sample have main ages at ca. 950 Ma to 1900 Ma. The zircon ages show, that the source areas for the Mesozoic sedimentary record changed clearly. We interpret the Paleozoic to Neoproterozoic ages of all samples as the influx of reworked local material, such as the Avalonian/Armorican basement units and the Variscan Basement. In our interpretation, the enormous amounts of Mesoproterozoic to upper Paleoproterozoic zircon ages in the Jurassic sample originated in the oceanic connection between Middle Europe and Baltica, as these specific zircon ages are typical for Baltica. This oceanic connection was

  14. LA-SF-ICP-MS zircon U-Pb geochronology of granitic rocks from the central Bundelkhand greenstone complex, Bundelkhand craton, India

    NASA Astrophysics Data System (ADS)

    Verma, Sanjeet K.; Verma, Surendra P.; Oliveira, Elson P.; Singh, Vinod K.; Moreno, Juan A.

    2016-03-01

    The central Bundelkhand greenstone complex in Bundelkhand craton, northern India is one of the well exposed Archaean supracrustal amphibolite, banded iron formation (BIF) and felsic volcanic rocks (FV) and associated with grey and pink porphyritic granite, tonalite-trondhjemite-granodiorite (TTG). Here we present high precision zircon U-Pb geochronological data for the pinkish porphyritic granites and TTG. The zircons from the grey-pinkish porphyritic granite show three different concordia ages of 2531 ± 21 Ma, 2516 ± 38 Ma, and 2514 ± 13 Ma, which are interpreted as the best estimate of the magmatic crystallization age for the studied granites. We also report the concordia age of 2669 ± 7.4 Ma for a trondhjemite gneiss sample, which is so far the youngest U-Pb geochronological data for a TTG rock suite in the Bundelkhand craton. This TTG formation at 2669 Ma is also more similar to Precambrian basement TTG gneisses of the Aravalli Craton of north western India and suggests that crust formation in the Bundelkhand Craton occurred in a similar time-frame to that recorded from the Aravalli craton of the North-western India.

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

    PubMed

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

    2006-06-15

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

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

    PubMed

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

    2006-06-15

    A laser ablation ICP-MS technique has been used to examine the radial distribution of lead in transverse sections of alligator femur. Annual bone growth in the femur results in the deposition of incremental layers of calcified tissue at the periphery of existing bone. Patterns of lead concentration within these layers provide a record of time-dependent accumulation from which exposure history can potentially be deduced. Femur specimens obtained from captive-reared alligators exhibited levels of lead accumulation that were entirely consistent with previously documented clinical signs of lead intoxication. In contrast, femurs obtained from wild alligators contained only minor amounts of lead that were likely accumulated as a result of incidental exposure. PMID:15982720

  17. New Sakmarian ages for the Rio Bonito formation (Paraná Basin, southern Brazil) based on LA-ICP-MS U-Pb radiometric dating of zircons crystals

    NASA Astrophysics Data System (ADS)

    Cagliari, Joice; Lavina, Ernesto Luiz Correa; Philipp, Ruy Paulo; Tognoli, Francisco Manoel Wohnrath; Basei, Miguel Angelo Stipp; Faccini, Ubiratan Ferrucio

    2014-12-01

    Two ash fall beds (tonstein) sampled from the post-glacial Permian deposits of the Paraná Basin have provided new U-Pb radiometric age constraints for this stratigraphic interval. The zircon grains were recovered from tonstein layers interbedded with fine-grained and carbonaceous lithologies in the middle portion of the Rio Bonito Formation. In both samples, the dominant population is interpreted as generated by explosive volcanism, as having formed immediately before the eruption. Based on 238U/206Pb, the selected zircon grains from the dominant population have weighted mean ages of 290.6 ± 2.8 Ma and 281.7 ± 3.2 Ma, corresponding to the Sakmarian and Kungurian ages in the Cisuralian epoch, respectively. These ages constrain the time of the deposition of the tonstein horizons and have important stratigraphic implications for the Late Paleozoic evolution of both the Paraná Basin and the southwestern region of Gondwana. The results presented here and the radiometric data already published suggest that deposition of the post-glacial coal-bearing deposits of the Rio Bonito Formation was probably initiated before the Early Permian. Thus, we infer that the climate had already ameliorated by this period in order to allow for the formation and accumulation of peat in this region of Gondwana.

  18. A multi-parametric microarray for protein profiling: simultaneous analysis of 8 different cytochromes via differentially element tagged antibodies and laser ablation ICP-MS.

    PubMed

    Waentig, Larissa; Techritz, Sandra; Jakubowski, Norbert; Roos, Peter H

    2013-11-01

    The paper presents a new multi-parametric protein microarray embracing the multi-analyte capabilities of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The combination of high throughput reverse phase protein microarrays with element tagged antibodies and LA-ICP-MS makes it possible to detect and quantify many proteins or biomarkers in multiple samples simultaneously. A proof of concept experiment is performed for the analysis of cytochromes particularly of cytochrome P450 enzymes, which play an important role in the metabolism of xenobiotics such as toxicants and drugs. With the aid of the LA-ICP-MS based multi-parametric reverse phase protein microarray it was possible to analyse 8 cytochromes in 14 different proteomes in one run. The methodology shows excellent detection limits in the lower amol range and a very good linearity of R(2) ≥ 0.9996 which is a prerequisite for the development of further quantification strategies.

  19. In situ LA-MC-ICP-MS U-Pb geochronology of igneous rocks in the Ashele Basin, Altay orogenic belt, northwest China: Constraints on the timing of polymetallic copper mineralization

    NASA Astrophysics Data System (ADS)

    Yang, Fuquan; Liu, Feng; Li, Qiang; Geng, Xinxia

    2014-01-01

    The Altay orogenic belt of Kazakhstan hosts a world-class polymetallic copper volcanogenic massive sulfide (VMS) metallogenic belt, and the eastern margin of this belt extends into the southern Chinese Altay. The Ashele Basin is located at the western end of the Chinese Altay and borders Kazakhstan. The basin hosts the large Ashele copper-zinc deposit, which is a typical VMS deposit and the largest deposit in the Ashele Basin, and it hosts the subvolcanic-hosted medium-sized Sarsuk polymetallic gold deposit. Both of these deposits are hosted in the Ashele Formation volcanic sequence. The Ashele copper-zinc orebodies are stratabound orebodies located between basalt and tuff units, and were formed during exhalative sediment deposition; in comparison, the Sarsuk gold-copper-lead-zinc orebodies are hosted by rhyolite porphyry that contains disseminated, veinlet, and veinlet-stockwork ore that formed during intrusion of the rhyolite porphyry. This study presents new zircon LA-MC-ICP-MS U-Pb analyses of six volcanic and subvolcanic units, and dikes associated with the Sarsuk and Ashele deposits. The ore-bearing rhyolite porphyry, diabase dike, basalt, tuff, and dacite porphyry samples analyzed during this study yielded ages of 382.0-382.8, 381.7, 388.2, 387.0, and 379.4 Ma, respectively. These data indicate that the Ashele Formation formed during the Early-Mid-Devonian (375-402 Ma), whereas the Ashele copper-zinc deposit formed during the Middle Devonian (388-387 Ma) and the Sarsuk polymetallic copper-gold deposit formed during the latest Middle Devonian (382 Ma). Inherited zircons within the six samples analyzed during this study yielded U-Pb ages of 618-2294 Ma, suggesting the presence of Precambrian crystalline basement within the Altay orogenic belt.

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

    NASA Astrophysics Data System (ADS)

    Boulyga, Sergei F.; Heumann, Klaus G.

    2005-04-01

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

  1. Recent applications on isotope ratio measurements by ICP-MS and LA-ICP-MS on biological samples and single particles

    NASA Astrophysics Data System (ADS)

    Becker, J. Sabine; Sela, Hagit; Dobrowolska, Justina; Zoriy, Miroslav; Becker, J. Susanne

    2008-02-01

    Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) have proved themselves to be powerful and sensitive inorganic mass spectrometric techniques for analysing stable and radioactive isotopes in different application fields because of their high sensitivity, low detection limits, good accuracy and precision. New applications of ICP-MS focus on tracer experiments and the development of isotope dilution techniques together with nanoflow injections for the analysis of small volumes of biological samples. Today, LA-ICP-MS is the method of choice for direct determination of metals, e.g., on protein bands in gels after the gel electrophoresis of protein mixtures. Tracer experiments using highly enriched 65Cu were utilized in order to study the formation of metal-binding bovine serum proteins. A challenging task for LA-ICP-MS is its application as an imaging mass spectrometric technique for the production of isotope images (e.gE, from thin sections of brain tissues stained with neodymium). In this paper, we demonstrate the application of imaging mass spectrometry on single particles (zircon and uranium oxide). Single Precambrian zircon crystals from the Baltic Shield were investigated with respect to isotope ratios using LA-ICP-MS for age dating. The U-Pb age was determined from the isochrone with (1.48 ± 0.14) × 109 a. Using isotope ratio measurements on 10 nuclear uranium oxide single particles the 235U/238U isotope ratio was determined to be 0.032 ± 0.004. This paper describes recent developments and applications of isotope ratio measurements by ICP-MS and LA-ICP-MS on biological samples and single particles.

  2. Plate interactions of Laurussia and Gondwana during the formation of Pangea- Constraints by U-Pb LA-SF-ICP-MS detrital zircon ages of Devonian and Early Carboniferous siliciclastics of the Rheinisches Schiefergebirge (Rhenohercynian zone, Central European

    NASA Astrophysics Data System (ADS)

    Eckelmann, Katja; Nesbor, Heinz-Dieter; Königshof, Peter; Linnemann, Ulf; Hofmann, Mandy; Lange, Jan-Michael; Sagawe, Anja

    2013-04-01

    The Rhenohercynian zone of the Central European Variscides contains top-NW thrusted rock complexes in the area of the Hörre nappe. Further to the north, par-authochthonous volcano-sedimentary complexes of the Lahn and Dill-Eder synclines occur. In our paper, a representative data set of U-Pb LA-SF ICP-MS ages of 1228 detrital zircon grains of Devonian and Lower Carboniferous sandstones from both areas is presented. The data constrain the Middle to Upper Devonian and the Lower Carboniferous siliciclastic and volcano-sedimentary complexes of the Hörre nappe to be allochtonous. The cluster of U-Pb ages of detrital zircon grains point to a provenance of the debris from the Saxo-Thuringian zone and rock complexes of the Mid-German Crystalline zone, which were formerly related to the latter one. A long-distance top-NW directed transport of the nappe complex in the Hörre nappe is required by our new data set. The zircon populations derived from the Saxo-Thuringian zone are representative for a Gondwanan hinterland and characterised by age clusters of ~530-700 Ma, ~1,8-2.2 Ga, ~2.5-2.7 Ga, and ~3.0-3.4 Ga. In a palaeogeographic view, the Saxo-Thuringian zone formed during Devonian to Lower Carboniferous time at the southern margin of the Rheic Ocean. A Lower Devonian sandstone sample from the par-authochtonous Lahn-Dill-Eder syncline shows a provenance, which is representative for Laurussia. Most of that debris seems to be derived from Baltica and Avalonia, two important parts of Laurussia. U-Pb zircon ages cluster at ~ 400-450 Ma, 540-650 Ma, 1.0-1.2 Ga, ~1.4-1.5 Ga, ~1.7-2.2 Ga, and 2.3-2.9 Ga. In terms of a palaeogeographic relation, these samples represent a sedimentary unit which was deposited at the northern margin of the Rheic Ocean at the edge of Laurussia facing to the south. Our data set constrains a top-SE directed subduction of the oceanic crust of the Rheic Ocean during its final closure and the formation of supercontinent Pangea.

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

    USGS Publications Warehouse

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

    2005-01-01

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

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

    PubMed

    Seltzer, Michaeld; Berry, Kristinh

    2005-03-01

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

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

    PubMed

    Seltzer, Michaeld; Berry, Kristinh

    2005-03-01

    The outer keratin layer (scute) of desert tortoise shells consists of incrementally grown laminae in which various bioaccumulated trace elements are sequestered during scute deposition. Laser ablation ICP-MS examination of laminae in scutes of dead tortoises revealed patterns of trace elemental distribution from which the chronology of elemental uptake can be inferred. These patterns may be of pathologic significance in the case of elemental toxicants such as arsenic, which has been linked to both shell and respiratory diseases. Laser ablation transects, performed along the lateral surfaces of sectioned scutes, offered the most successful means of avoiding exogenous contamination that was present on the scute exterior. Semiquantitative determination of elemental concentrations was achieved using sulfur, a keratin matrix element, as an internal standard. The results presented here highlight the potential of laser ablation ICP-MS as a diagnostic tool for investigating toxic element uptake as it pertains to tortoise morbidity and mortality. PMID:15740773

  6. Comparative Investigation between In Situ Laser Ablation Versus Bulk Sample (Solution Mode) Inductively Coupled Plasma Mass Spectrometry (ICP-MS) Analysis of Trinitite Post-Detonation Materials.

    PubMed

    Dustin, Megan K; Koeman, Elizabeth C; Simonetti, Antonio; Torrano, Zachary; Burns, Peter C

    2016-09-01

    In the event of the interception of illicit nuclear materials or detonation of a nuclear device, timely and accurate deciphering of the chemical and isotopic composition of pertinent samples is pivotal in enhancing both nuclear security and source attribution. This study reports the results from a first time (to our knowledge), detailed comparative investigation conducted of Trinitite post-detonation materials using both solution mode (SM) and laser ablation (LA) inductively coupled plasma mass spectrometry (ICP-MS) techniques. Trace element abundances determined for bulk Trinitite samples subsequent to digestion and preparation for SM-ICP-MS analysis compare favorably to calculated median concentrations based on LA-ICP-MS analyses for the identical samples. The trace element concentrations obtained by individual LA-ICP-MS analyses indicate a large scatter compared to the corresponding bulk sample SM-ICP-MS results for the same sample; this feature can be attributed to the incorporation into the blast melt of specific, precursor accessory minerals (minerals in small quantities, such as carbonates, sulfates, chlorites, clay, and mafic minerals) present at ground zero. The favorable comparison reported here validates and confirms the use of the LA-ICP-MS technique in obtaining accurate forensic information at high spatial resolution in nuclear materials for source attribution purposes. This investigation also reports device-like (240)Pu/(239)Pu ratios (∼0.022) for Pu-rich regions of the blast melt that are also characterized by higher Ca and U contents, which is consistent with results from previous studies. PMID:27566253

  7. Trace elemental analysis of automotive paints by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS).

    PubMed

    Hobbs, Andria L; Almirall, José R

    2003-08-01

    Paints and coatings are frequently encountered as types of materials that are submitted to forensic science laboratories as a result of trace evidence transfers. The aim of this study was to develop a method to complement the commonly used techniques in a forensic laboratory in order to better characterize these samples for forensic purposes. A laser ablation method has been used to simultaneously sample several layers directly prior to introduction into an inductively coupled plasma-mass spectrometer for the detection and quantification of the trace metals present in the layer(s). Time-resolved analysis plots displaying the elemental response and quantification of selected metals are compared to associate/discriminate paint samples. Matrix-matched standards were successfully incorporated into the analysis scheme for quantification of lead in the solid paint samples. Preparation of new matrix-matched standards for quantification of additional elements developed for this study are also presented. A sample set of eighteen (18) survey automotive paint samples have been analyzed with the developed method in order to determine the utility of LA-ICP-MS for trace element analysis of paints.

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

    PubMed

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

    2015-10-01

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

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

    PubMed

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

    2015-10-01

    We enhanced an existing technique, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), to function as a non-lethal tool in the temporal characterization of trace element exposure in wild mammals. Mercury (Hg), copper (Cu), cadmium (Cd), lead (Pb), iron (Fe) and zinc (Zn) were analyzed along the hair of captive and wild grizzly bears (Ursus arctos horribilis). Laser parameters were optimized (consecutive 2000 μm line scans along the middle line of the hair at a speed of 50 μm/s; spot size=30 μm) for consistent ablation of the hair. A pressed pellet of reference material DOLT-2 and sulfur were used as external and internal standards, respectively. Our newly adapted method passed the quality control tests with strong correlations between trace element concentrations obtained using LA-ICP-MS and those obtained with regular solution-ICP-MS (r(2)=0.92, 0.98, 0.63, 0.57, 0.99 and 0.90 for Hg, Fe, Cu, Zn, Cd and Pb, respectively). Cross-correlation analyses revealed good reproducibility between trace element patterns obtained from hair collected from the same bear. One exception was Cd for which external contamination was observed resulting in poor reproducibility. In order to validate the method, we used LA-ICP-MS on the hair of five captive grizzly bears fed known and varying amounts of cutthroat trout over a period of 33 days. Trace element patterns along the hair revealed strong Hg, Cu and Zn signals coinciding with fish consumption. Accordingly, significant correlations between Hg, Cu, and Zn in the hair and Hg, Cu, and Zn intake were evident and we were able to develop accumulation models for each of these elements. While the use of LA-ICP-MS for the monitoring of trace elements in wildlife is in its infancy, this study highlights the robustness and applicability of this newly adapted method. PMID:26005744

  10. Tectonic attribution of the Langshan area in western Inner Mongolia and implications for the Neoarchean-Paleoproterozoic evolution of the Western North China Craton: Evidence from LA-ICP-MS zircon U-Pb dating of the Langshan basement

    NASA Astrophysics Data System (ADS)

    Wang, Zeng-Zhen; Han, Bao-Fu; Feng, Li-Xia; Liu, Bo; Zheng, Bo; Kong, Ling-Jie

    2016-09-01

    The Langshan area in western Inner Mongolia, China, is situated on the conjunction of the Alxa Block in the west, the northern North China Craton (NCC) in the east, and the Central Asian Orogenic Belt in the north, but its tectonic attribution has long been in debate, because the Alxa Block may be an independent Precambrian block from the NCC and the boundary between the two blocks may lie along the Bayanwulashan, to the west of the Langshan, instead of around the Helanshan area, to the east of the Langshan. In this study, new LA-ICP-MS zircon U-Pb ages of four gneisses, one amphibolite, and three granites, combined with previously published age data from Langshan basement rocks, indicate that the Langshan area may be subdivided into the Main Langshan, to the north of a series of NNW-trending faults, and the Southern Langshan in the south. The Main Langshan basement rocks were mainly formed during Neoarchean-Paleoproterozoic, with five major stages of ~ 2.7 Ga (2686 Ma), ~ 2.6 Ga (2619-2563 Ma), ~ 2.5 Ga (2534-2491 Ma), ~ 1.95 Ga (1969-1938 Ma), and ~ 1.7 Ga (1672 Ma). These stages are largely consistent with the major tectonothermal events of the northern NCC during Neoarchean-Paleoproterozoic but significantly different from the principal formation period (ca. 2.5-1.9 Ga) of Alxa basement rocks. The Southern Langshan is characterized by the presence of late Paleoproterozoic (~ 1.9 Ga) and Neoproterozoic (~ 0.9 Ga) rocks, and the latter is consistent with the Neoproterozoic magmatism in central Alxa Block, which might be formed in a orogenesis-related compressional environment, in contrast to contemporaneous rift-related extensional tectonic setting within the NCC. Therefore, the Main Langshan and the Southern Langshan are most likely closely related to the northern NCC and the Alxa Block, respectively.

  11. Characterization of depositional age and structure of sedimentary successions by U-Pb TIMS and LA-ICP-MS dating of volcanic horizons and detrital zircons: an example from the western Trondheim Nappe Complex, Scandinavian Caledonides

    NASA Astrophysics Data System (ADS)

    Gasser, Deta; Grenne, Tor; Corfu, Fernando; Eivind Augland, Lars

    2016-04-01

    Revealing the absolute depositional age of non-fossiliferous sedimentary successions represents a long-lasting challenge in Earth Sciences. Lacking age control hampers the correct interpretation of the temporal evolution of depositional systems, and, if deformed, of the architecture of fold-and-thrust belts. Dating of detrital zircons within clastic sedimentary successions has over the past decades become a popular method to approximate the absolute depositional age and to characterize the source areas of such rocks. If combined with other geochronological information, such as dating of contemporaneous volcanic horizons, a much better resolution of the stratigraphy and structure of non-fossiliferous sedimentary successions can be achieved. The western Trondheim nappe complex in the central Scandinavian Caledonides is a classical area in this respect. On top of Late Cambrian to Early Ordovician ophiolitic fragments, various volcanic, volcano-clastic and clastic successions tell a complex story of island-arc formation, ocean closure and continent collision. Several famous fossil horizons indicate deposition during the Middle to Upper Ordovician (ca. 470-445 Ma), but large areas lack an absolute age control and several contrasting stratigraphic schemes and structural interpretations have been presented in the past. In this contribution we present the results of LA-ICP-MS detrital U-Pb zircon dating of clastic horizons as well as U-Pb TIMS zircon dating of volcanic horizons and magmatic clasts in conglomerates in order to characterize the depositional age and structure of the western Trondheim nappe complex in more detail. Together with field observations, including way up criteria, the zircon data enable significant revisions of existing stratigraphic and structural models. At least four (volcano-)sedimentary successions can be distinguished above the ca. 480-485 Ma greenstones: (1) ca. 470-463 Ma shales, limestones and andesitic porphyrites (Hølonda and Fanabekken

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

    NASA Astrophysics Data System (ADS)

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

    2003-09-01

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

  13. Spatially resolved analysis of plutonium isotopic signatures in environmental particle samples by laser ablation-MC-ICP-MS.

    PubMed

    Konegger-Kappel, Stefanie; Prohaska, Thomas

    2016-01-01

    Laser ablation-multi-collector-inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) was optimized and investigated with respect to its performance for determining spatially resolved Pu isotopic signatures within radioactive fuel particle clusters. Fuel particles had been emitted from the Chernobyl nuclear power plant (ChNPP) where the 1986 accident occurred and were deposited in the surrounding soil, where weathering processes caused their transformation into radioactive clusters, so-called micro-samples. The size of the investigated micro-samples, which showed surface alpha activities below 40 mBq, ranged from about 200 to 1000 μm. Direct single static point ablations allowed to identify variations of Pu isotopic signatures not only between distinct fuel particle clusters but also within individual clusters. The resolution was limited to 100 to 120 μm as a result of the applied laser ablation spot sizes and the resolving power of the nuclear track radiography methodology that was applied for particle pre-selection. The determined (242)Pu/(239)Pu and (240)Pu/(239)Pu isotope ratios showed a variation from low to high Pu isotope ratios, ranging from 0.007(2) to 0.047(8) for (242)Pu/(239)Pu and from 0.183(13) to 0.577(40) for (240)Pu/(239)Pu. In contrast to other studies, the applied methodology allowed for the first time to display the Pu isotopic distribution in the Chernobyl fallout, which reflects the differences in the spent fuel composition over the reactor core. The measured Pu isotopic signatures are in good agreement with the expected Pu isotopic composition distribution that is typical for a RBMK-1000 reactor, indicating that the analyzed samples are originating from the ill-fated Chernobyl reactor. The average Pu isotope ratios [(240)Pu/(239)Pu = 0.388(86), (242)Pu/(239)Pu = 0.028(11)] that were calculated from all investigated samples (n = 48) correspond well to previously published results of Pu analyses in contaminated samples from

  14. Spatially resolved analysis of plutonium isotopic signatures in environmental particle samples by laser ablation-MC-ICP-MS.

    PubMed

    Konegger-Kappel, Stefanie; Prohaska, Thomas

    2016-01-01

    Laser ablation-multi-collector-inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) was optimized and investigated with respect to its performance for determining spatially resolved Pu isotopic signatures within radioactive fuel particle clusters. Fuel particles had been emitted from the Chernobyl nuclear power plant (ChNPP) where the 1986 accident occurred and were deposited in the surrounding soil, where weathering processes caused their transformation into radioactive clusters, so-called micro-samples. The size of the investigated micro-samples, which showed surface alpha activities below 40 mBq, ranged from about 200 to 1000 μm. Direct single static point ablations allowed to identify variations of Pu isotopic signatures not only between distinct fuel particle clusters but also within individual clusters. The resolution was limited to 100 to 120 μm as a result of the applied laser ablation spot sizes and the resolving power of the nuclear track radiography methodology that was applied for particle pre-selection. The determined (242)Pu/(239)Pu and (240)Pu/(239)Pu isotope ratios showed a variation from low to high Pu isotope ratios, ranging from 0.007(2) to 0.047(8) for (242)Pu/(239)Pu and from 0.183(13) to 0.577(40) for (240)Pu/(239)Pu. In contrast to other studies, the applied methodology allowed for the first time to display the Pu isotopic distribution in the Chernobyl fallout, which reflects the differences in the spent fuel composition over the reactor core. The measured Pu isotopic signatures are in good agreement with the expected Pu isotopic composition distribution that is typical for a RBMK-1000 reactor, indicating that the analyzed samples are originating from the ill-fated Chernobyl reactor. The average Pu isotope ratios [(240)Pu/(239)Pu = 0.388(86), (242)Pu/(239)Pu = 0.028(11)] that were calculated from all investigated samples (n = 48) correspond well to previously published results of Pu analyses in contaminated samples from

  15. The Cadomian Orogeny and the opening of the Rheic Ocean: The diacrony of geotectonic processes constrained by LA-ICP-MS U Pb zircon dating (Ossa-Morena and Saxo-Thuringian Zones, Iberian and Bohemian Massifs)

    NASA Astrophysics Data System (ADS)

    Linnemann, Ulf; Pereira, Francisco; Jeffries, Teresa E.; Drost, Kerstin; Gerdes, Axel

    2008-12-01

    Cadomian orogenic processes and their continuum to the opening of the Rheic Ocean were modeled by making use of new LA-ICP-MS U-Pb ages from detrital zircons of sedimentary rocks of Late Neoproterozoic (Ediacaran) and Cambro-Ordovician sediments of the Ossa-Morena Zone (Iberian Massif) compared with those from the Saxo-Thuringian Zones (Bohemian Massif). Presented data constrain a diachrony of Cadomian and related geotectonic processes along the northern realm of the Gondwana Supercontinent. Early stage of Cadomian evolution is characterized by a continental magmatic arc at the periphery of the West African Craton and a related back-arc basin opened at c. 590 to 570 Ma. Diacronic arc-continent collision was caused by oblique vector of subduction and started first in the East of Peri-Gondwana at c. 560-570 Ma and resulted at c. 543 Ma in the formation of a short-lived Cadomian retro-arc basin in the Saxo-Thuringian Zone. In contrast, more to the West in the Ossa-Morena Zone, the Cadomian back-arc basin was longer active, at least until c. 545 Ma. In that region, final magmatic pulse of the Cadomian magmatic arc at c. 550 Ma is documented by new zircon data. Closure of the Cadomian back-arc basin and arc-continent collision in the Ossa-Morena Zone occurred between c. 545 Ma and the overall onset of Cambrian plutonism at c. 540 Ma. A mid-oceanic ridge was subducted underneath the Cadomian orogen accompanied by slab break-off of the subducted oceanic plate. Oblique incision of the oceanic ridge into the continent caused the formation of rift basins during the Lower to Middle Cambrian (c. 530-500 Ma). This process continued and finally caused the opening of the Rheic Ocean documented by thick Lower Ordovician siliciclastic sediments and a final magmatic event at c. 490-485 Ma. Opening of the Cambrian rift basin and of the Rheic Ocean again was diachronic and started from the West of Peri-Gondwana and expanded eastward.

  16. A novel quantification strategy of transferrin and albumin in human serum by species-unspecific isotope dilution laser ablation inductively coupled plasma mass spectrometry (ICP-MS).

    PubMed

    Feng, Liuxing; Zhang, Dan; Wang, Jun; Shen, Dairui; Li, Hongmei

    2015-07-16

    Species-specific (SS) isotope dilution analysis with gel electrophoresis (GE)-laser ablation (LA)-ICP-MS is a promising technique for the quantification of particular metal-binding proteins in biological samples. However, unavailable isotopically enriched spike and metal losses in GE separation are main limitations for SS-isotope dilution PAGE-LA-ICP-MS. In this study, we report for the first time the absolute quantification of transferrin (Tf) and albumin (Alb) in human serum by non-denaturing (native) GE combined with species-unspecific isotope dilution mass spectrometry (IDMS). In order to achieve a homogeneous distribution of both protein and isotope-enriched spike (simulated isotope equilibration), immersing the protein strips with (34)S spike solution after gel electrophoresis was demonstrated to be an effective way of spike addition. Furthermore, effects of immersion time and (34)S spike concentration were investigated to obtain optimal conditions of the post-electrophoresis isotope dilution method. The relative mass of spike and ablated sample (m(sp)/m(sam)) in IDMS equation was calculated by standard Tf and Alb proteins, which could be applied to the quantification of Tf and Alb in ERM-DA470k/IFCC for method confirmation. The results were in agreement with the certified value with good precision and small uncertainty (1.5-3%). In this method, species-specific spike protein is not necessary and the integrity of the heteroatom-protein could be maintained in sample preparation process. Moreover, the application of species-unspecific isotope dilution GE-LA-ICP-MS has the potential to offer reliable, direct and simultaneous quantification of proteins after conventional 1D and 2D gel electrophoretic separations.

  17. A laser ablation ICP-MS based method for multiplexed immunoblot analysis: applications to manganese-dependent protein dynamics of photosystem II in barley (Hordeum vulgare L.).

    PubMed

    de Bang, Thomas Christian; Petersen, Jørgen; Pedas, Pai Rosager; Rogowska-Wrzesinska, Adelina; Jensen, Ole Noerregaard; Schjoerring, Jan Kofod; Jensen, Poul Erik; Thelen, Jay J; Husted, Søren

    2015-08-01

    Manganese (Mn) constitutes an essential co-factor in the oxygen-evolving complex of photosystem II (PSII). Consequently, Mn deficiency reduces photosynthetic efficiency and leads to changes in PSII composition. In order to study these changes, multiplexed protein assays are advantageous. Here, we developed a multiplexed antibody-based assay and analysed selected PSII subunits in barley (Hordeum vulgare L.). A selection of antibodies were labelled with specific lanthanides and immunoreacted with thylakoids exposed to Mn deficiency after western blotting. Subsequently, western blot membranes were analysed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), which allowed selective and relative quantitative analysis via the different lanthanides. The method was evaluated against established liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) methods, based on data-dependent acquisition (DDA) and selected reaction monitoring (SRM). Manganese deficiency resulted in a general decrease in PSII protein abundances, an effect that was shown to be reversible upon Mn re-supplementation. Specifically, the extrinsic proteins PsbP and PsbQ showed Mn-dependent changes in abundances. Similar trends in the response to Mn deficiency at the protein level were observed when comparing DDA, SRM and LA-ICP-MS results. A biologically important exception to this trend was the loss of PsbO in the SRM analysis, which highlights the necessity of validating protein changes by more than one technique. The developed method enables a higher number of proteins to be multiplexed in comparison to existing immunoassays. Furthermore, multiplexed protein analysis by LA-ICP-MS provides an analytical platform with high throughput appropriate for screening large collections of plants.

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

    PubMed

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

    2013-05-01

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

  19. ICP-MS Workshop

    SciTech Connect

    Carman, April J.; Eiden, Gregory C.

    2014-11-01

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

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

    PubMed

    Boulyga, Sergei F; Prohaska, Thomas

    2008-01-01

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

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

    PubMed

    Boulyga, Sergei F; Prohaska, Thomas

    2008-01-01

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

  2. Isotopic ratio measurements with ICP-MS

    SciTech Connect

    Russ, G.P. III; Bazan, J.M.

    1986-06-03

    An inductively-coupled-plasma source mass spectrometer (ICP-MS) has been used to measure the isotopic composition of U, Pb, Os, and B standards. Particular emphasis has been placed on uranium because of its nuclear and environmental interest and because of the availability of a well-characterized set of standards with a wide range of isotopic compositions. The precision and accuracy obtainable in isotope ratio measurements by ICP-MS depend on many factors including background, interferences, dead time, mass fractionation (bias), abundance sensitivity, and counting statistics. Which, if any, of these factors controls accuracy and precision depends on the type of sample being analyzed and the characteristics of the mass spectrometer. These issues are discussed in detail.

  3. Determination of impurities in thoria (ThO 2) using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS)

    NASA Astrophysics Data System (ADS)

    Alamelu, Devanathan; Choudhary, Ashwini Kumar; Aggarwal, Suresh Kumar

    2010-11-01

    Elemental impurities in nuclear grade thoria were determined using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) employing ArF laser (20 ns, 193 nm, 20 Hz). Three certified standards of thoria, prepared in the Department of Atomic Energy (DAE), India were used for this work. Magnesium was used as an internal standard for quantification in view of its addition during fuel fabrication. The concentrations determined for 16 different elements (Al, B, Cd, Ce, Cu, Dy, Er, Eu, Fe, Gd, Mg, Mn, Mo, Ni, Sb, Sm and V), spanning four orders of magnitude, were within 20% of the certified values in the standards. The methodology is of interest to reduce the analytical effort with regard to dissolution of thoria samples, avoid the production of radioactive liquid waste streams and relatively simple mass spectrum as compared to complex emission spectra in atomic emission spectroscopy (AES) and laser induced breakdown spectroscopy (LIBS). The development and validation of analytical methodologies based on independent physico-chemical principles is of great relevance to characterize the in-house prepared working standards for routine applications.

  4. Laser Ablation in situ (U-Th-Sm)/He and U-Pb Double-Dating of Apatite and Zircon: Techniques and Applications

    NASA Astrophysics Data System (ADS)

    McInnes, B.; Danišík, M.; Evans, N.; McDonald, B.; Becker, T.; Vermeesch, P.

    2015-12-01

    We present a new laser-based technique for rapid, quantitative and automated in situ microanalysis of U, Th, Sm, Pb and He for applications in geochronology, thermochronometry and geochemistry (Evans et al., 2015). This novel capability permits a detailed interrogation of the time-temperature history of rocks containing apatite, zircon and other accessory phases by providing both (U-Th-Sm)/He and U-Pb ages (+trace element analysis) on single crystals. In situ laser microanalysis offers several advantages over conventional bulk crystal methods in terms of safety, cost, productivity and spatial resolution. We developed and integrated a suite of analytical instruments including a 193 nm ArF excimer laser system (RESOlution M-50A-LR), a quadrupole ICP-MS (Agilent 7700s), an Alphachron helium mass spectrometry system and swappable flow-through and ultra-high vacuum analytical chambers. The analytical protocols include the following steps: mounting/polishing in PFA Teflon using methods similar to those adopted for fission track etching; laser He extraction and analysis using a 2 s ablation at 5 Hz and 2-3 J/cm2fluence; He pit volume measurement using atomic force microscopy, and U-Th-Sm-Pb (plus optional trace element) analysis using traditional laser ablation methods. The major analytical challenges for apatite include the low U, Th and He contents relative to zircon and the elevated common Pb content. On the other hand, apatite typically has less extreme and less complex zoning of parent isotopes (primarily U and Th). A freeware application has been developed for determining (U-Th-Sm)/He ages from the raw analytical data and Iolite software was used for U-Pb age and trace element determination. In situ double-dating has successfully replicated conventional U-Pb and (U-Th)/He age variations in xenocrystic zircon from the diamondiferous Ellendale lamproite pipe, Western Australia and increased zircon analytical throughput by a factor of 50 over conventional methods

  5. 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.

  6. Structural characteristics and LA-ICP-MS U-Pb zircon geochronology of the deformed granitic rocks from the Mesozoic Xingcheng-Taili ductile shear zone in the North China Craton

    NASA Astrophysics Data System (ADS)

    Liang, Chenyue; Liu, Yongjiang; Neubauer, Franz; Jin, Wei; Zeng, Zuoxun; Genser, Johann; Li, Weimin; Li, Wei; Han, Guoqing; Wen, Quanbo; Zhao, Yingli; Cai, Libin

    2015-05-01

    We describe the recently detected ENE-trending Xingcheng-Taili ductile strike-slip shear zone, which is an important Mesozoic low- to middle-grade tectonic element formed during the reactivation of the North China Craton (NCC) at the eastern termination of the Yanshanian orogenic belt. Within the Xingcheng-Taili ductile shear zone, the degree of deformation weakens gradually from NW to SE. Three main types of banded granitic gneisses represent low- to middle-grade metamorphic tectonites. New U-Pb zircon dating gives a wide range of protolith ages. Neoarchean granitic rocks with an emplacement age of 2498.4 ± 6.3 Ma have obvious E-W trending banded structures. Upper Triassic granitic rocks with U-Pb zircon ages of 219.7 ± 1.1 Ma, 218.74 ± 0.61 Ma, 212.1 ± 1.6 Ma and 212.3 ± 1.9 Ma are considered to relate to the collision of the NCC and Yangtze craton in early Mesozoic times. The emplacement of biotite adamellite bodies with ages of 159.0 ± 0.8 Ma and 152.4 ± 1.9 Ma is related to the thinning of the NCC's continental crust. An ENE-trending sinistral ductile shear zone developed within these granites. The strongly deformed biotite adamellite bodies bear a gneissosity with S-C fabrics, ENE-trending sinistral shear zones and show the deformation characteristics of a shallow crustal level, reflecting decratonization of the NCC. Crystal lattice preferred orientations (LPO) of quartz, determined by electron back-scatter diffraction, suggest sinistral strike-slip shear and a deformation temperature at about 400 to 500 °C. Quartz mainly shows low-temperature fabrics with a dominant {0001}-slip system similar to the temperature estimated by the micro-structural characteristics of quartz and feldspar. This deformation event might have occurred in Early Cretaceous times and is related to the lithospheric thinning and extension of the North China Craton triggered by an ongoing roll-back of the Pacific Plate beneath the eastern North China Craton.

  7. Zircon U-Pb Age Distributions in Cogenetic Crystal-Rich Dacitic and Crystal-Poor Rhyolitic Members of Zoned Ignimbrites in the Southern Rocky Mountains by Chemical Abrasion Inductively-Coupled-Plasma Mass Spectrometry (CA-LA-ICP-MS).

    NASA Astrophysics Data System (ADS)

    Sliwinski, J.; Zimmerer, M. J.; Guillong, M.; Bachmann, O.; Lipman, P. W.

    2015-12-01

    The San Juan locus of the Southern Rocky Mountain Volcanic Field (SRMVF) in SW Colorado represents an erosional remnant of a mid-Tertiary (~37-23 Ma) ignimbrite flare up that produced some of the most voluminous ignimbrites on Earth. A key feature of many SRMVF ignimbrites is compositional zonation, with many volcanic units comprising both dacitic and rhyolitic horizons. Geochemical, field and petrographic evidence suggests that dacites and rhyolites are cogenetic. Here, we report U-Pb zircon ages by chemical abrasion inductively-coupled-plasma mass spectrometry (CA-LA-ICPMS) for rhyolitic and dacitic components in four units: the Bonanza, Rat Creek, Carpenter Ridge and Nelson Mountain Tuffs. All units show zircon age spectra that are either within analytical uncertainty of Ar/Ar ages or are appreciably older, indicating prolonged magma residence times (~500 ka) prior to eruption. Anomalously young Pb-loss zones in zircon have been largely removed by chemical abrasion. Older, inherited zircons and zircon cores (60-2000 Ma) are rare in all samples, suggesting limited assimilation of upper crustal Precambrian country rock or complete resorption during recharge events and magma chamber growth.

  8. Geochemical applications of the tandem LA-ICP-MS/LIBS analytical technique

    NASA Astrophysics Data System (ADS)

    Guitreau, M.; Gonzalez, J. J.; Mukasa, S. B.; Colucci, M. T.

    2013-12-01

    Improvements in Laser Ablation for material sampling over the past few decades have led to the emergence of several applications of this in-situ technique to some important geochemical measurements. The technique is commonly used for both elemental [1] and isotopic analyses [2], and has multiple advantages compared to dissolution techniques, notably higher spatial resolution, easier and faster sample preparation, and for many applications a non-destructive method. A significant advantage of this technique in geochemistry is full characterization of a sample (e.g., glass or mineral) using a single spot of limited size (i.e., 20-80 μm) to eliminate or minimize complexities due to potential chemical zonations. Major advancement is being realized in the analysis of volcanic glasses for their elemental and volatile concentrations as well as zircon elemental and U-Pb isotopic compositions using a new approach that combines the capabilities of the two most common laser ablation modalities; LA-ICP-MS/LIBS, which stands for Laser Ablation Inductively Coupled Plasma Mass Spectrometry/Laser Induced Breakdown Spectroscopy. LIBS is based on direct measurement of the optical emission originating from the laser-induced plasma [3] whereas LA-ICP-MS involves transport and excitation of the ablated aerosol to a secondary source (ICP), before entering a mass spectrometer [4]. Analysis by these two techniques can complement each other quite well, as every laser pulse for ablation provides the optical plasma for emission spectroscopy and particles for ICP mass spectrometry. We will present data demonstrating that rare-earth element (REE) concentrations can be determined using LIBS in both zircon and volcanic glasses. In addition, we have promising, provisional hydrogen concentration data measured concurrently with the REE in volcanic glasses, which is not possible using only LA-ICP-MS.

  9. The evolution of the neoproterozoic São Gabriel juvenile terrane, southern Brazil based on SHRIMP and LA-ICP-MS U-Pb ages and ?18O data on detrital zircon

    NASA Astrophysics Data System (ADS)

    Lena, L. O.; Pimentel, M. M.; Philipp, R. P.; Armstrong, R. A.; Sato, K.

    2013-12-01

    The São Gabriel terrane is a segment of juvenile crust exposed in the western part of the Dom Feliciano Belt in the southern Mantiqueira Province, southern Brazil. In this study, SHRIMP and LA-ICPMS U-Pb geochronological data for 171 detrital zircons of the Cambaizinho Complex are used to investigate the tectonic evolution of this juvenile terrain. Eighty-one grains were later selected for SIMS δ18O analyses. Ages ranged from 840 to 660 Ma, with a strong concentration between ca. 750 and 700 Ma. The age spectrum of the detrital zircon grains from this meta-sedimentary succession suggests that the original sediments were derived from the erosion of the arc, most likely in a short-lived syn-orogentic basin. Th/U ratios and internal structures of the zircon grains reveal that they were mostly eroded from the arc magmatic rocks, without any relevant contribution from their metamorphic counterparts, or from any other older source. The δ18O values varied from 3.2 to 9.6‰, indicating the coeval crystallization of both unaltered, pristine mantle magmas alongside altered mantle magmas, and strongly contaminated continental crustal magmas generated in both continental and oceanic arc setting. Three periods in the progressive evolution of the terrane were recognized: Period I is represented by the installation of an island-arc subduction zone. The data set suggest that this period started at ca. 840 Ma and went on until 750 Ma. In this period δ18O values varied between 3.2 to 5.5 ‰, suggesting the crystallization of normal mantle-derived magmas, and juvenile magmas with assimilation of hydrothermally altered crust. Period II took place between ca. 750-690 Ma, which represents the peak of magmatic activity suggested by the large abundance of detrital zircons in the probability density diagrams. Here, δ18O values ranged from 4.0 to 9.4 ‰. The wide range of δ18O values reveals the coexistence of magmas with continental, mantle, and altered mantle isotopic signatures

  10. The oldest sediments of Greece revealed by detrital zircon LA-ICP-MS U-Pb dating: Cambro-Ordovician sandstones from northern Gondwana in the External Hellenides - implications on the evolution of the eastern Mediterranean

    NASA Astrophysics Data System (ADS)

    Kydonakis, Konstantinos; Kostopoulos, Dimitrios; Poujol, Marc; Brun, Jean-Pierre; Papanikolaou, Dimitrios; Paquette, Jean-Louis

    2013-04-01

    Detrital zircon U-Pb ages of a quartzite from the Feneos locality of Peloponnesus, S. Greece, were determined by LA-ICPMS. The rock classifies as a mature quartz arenite and belongs to an original shale-sandstone succession now metamorphosed into a phyllite-quartzite unit. The latter chiefly represents the External Blueschist Belt of the Hellenides widely known as the Arna or Phyllite - Quartzite (PQ) Unit. Zircon age clusters at 0.5-0.75, 0.85, 0.95-1.1, 1.75-2 and 2.4-3 Ga point at the Saharan Metacraton and the Transgondwanan Supermountain as contributing sources; the youngest concordant grain is 522 Ma old. Based on great similarities in lithology, zircon age-distribution patterns and depositional setting between the Feneos quartzite and intact Cambro-Ordovician sandstone-shale sequences of Libya (Murzuq and Kufrah basins) we propose that the protolith of the former was deposited in an epeiric sea north of Libya during the Cambro-Ordovician. Feneos, as part of the Cimmerian block, had become detached from the NE Gondwanan margin during Late Carboniferous - Early Permian times and drifted northward. In central Crete, similar-looking sequences (Galinos beds) were originally deposited in an accretionary/fore-arc complex outboard of the south Laurussian active margin (Pelagonia) between ~297-230 Ma. The southern Pelagonian margin eventually collided (mild docking) with the northward drifting Cimmerian block signaling the closure of Palaeotethys by early Late Triassic. The Gondwanan affinity of the Feneos quartzite strongly contrasts the European one of the Galinos beds; the suture of Palaeotethys can thus be traced in S. Greece within the pre-Triassic sedimentary sequences of Peloponnesus and Crete. In the eastern Mediterranean realm, rocks with similar age clusters crop out in Greece (Peloponnesus, this study; eastern Crete, Sfaka locality; north-central Macedonia, Vertiskos terrane), NW Turkey (central Sakarya terrane), Libya (Murzuq and Kufrah basins), Israel

  11. Geochemistry of the Spor Mountain rhyolite, western Utah, as revealed by laser ablation ICP-MS, cathodoluminescence, and electron microprobe analysis

    NASA Astrophysics Data System (ADS)

    Dailey, S. R.; Christiansen, E. H.; Dorais, M.; Fernandez, D. P.

    2015-12-01

    The Miocene topaz rhyolite at Spor Mountain in western Utah hosts one of the largest beryllium deposits in the world and was responsible for producing 85% of the beryllium mined worldwide in 2010 (Boland, 2012). The Spor Mountain rhyolite is composed primarily of Ca-poor plagioclase (An8), sodic sanidine (Or40), Fe-rich biotite (Fe/(Fe+Mg)>0.95; Al 1.2-1.4 apfu), and Ti-poor quartz, along with several trace-element rich accessory phases including zircon, monazite, thorite, columbite, and allanite. Cathodoluminescence (CL) studies of quartz show oscillatory zoning, with 80% of the examined crystals displaying euhedral edges and slightly darker rims. CL images were used to guide laser ablation (LA) ICP-MS analysis of quartz, along with analyses of plagioclase, sanidine, biotite, and glass. Ti concentrations in quartz are 20±6 ppm; there is no quantifiable variation of Ti from core to rim within the diameter of the laser spot (53 microns). Temperatures, calculated using Ti in quartz (at 2 kb, aTiO2=0.34), vary between 529±10 C (Thomas et al., 2011), 669±13 C (Huang and Audetat, 2012), and 691±13 C (Wark and Watson, 2006). Two feldspar thermometry yield temperatures of 686±33 C (Elkins and Grove, 1990) and 670±41 C (Benisek et al., 2010). Zr saturation temperatures (Watson and Harrison, 1983) average 711±28 C. Analysis of the glass reveal the Spor Mountain rhyolite is greatly enriched in rare elements (i.e. Li, Be, F, Ga, Rb, Nb, Mo, Sn, and Ta) compared to average continental crust (Rudnick and Gao, 2003). Be in the glass can have as much as 100 ppm, nearly 50 times the concentration in continental crust. REE partition coefficients for sanidine are 2 to 3 times higher in the Spor Mountain rhyolite when compared to other silicic magmas (Nash and Crecraft, 1985; Mahood and Hildreth, 1983), although plagioclase tends to have lower partition coefficients; biotite has lower partition coefficients for LREE and higher partition coefficients for HREE. The patterns of

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

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

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

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

    USGS Publications Warehouse

    Nadoll, P.; Koenig, A.E.

    2011-01-01

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

  14. Apatite fission track dating by LA-ICP-MS and External Detector Method: How do they stack up?

    NASA Astrophysics Data System (ADS)

    Seiler, C.; Gleadow, A. J.; Kohn, B. P.

    2013-12-01

    Analysis of trace element compositions by laser ablation ICP-MS has become a widely used tool to determine in-situ ages in geochronology. Although used primarily for U-Pb dating, LA-ICP-MS has been successfully adapted to other dating techniques such as apatite fission track (Hasebe et al., 2004) or (U-Th)/He (Boyce et al., 2006), making it an ideal tool for multi-system thermochronological studies. LA-ICP-MS fission track dating has several important advantages over the traditional external detector method (EDM), particularly in terms of sample turn-around time and the fact that neutron irradiations (and the handling of radioactive materials) are no longer necessary, while providing a similar level of in-situ information. Perhaps the most important benefits of LA-ICP-MS fission track dating is that it could potentially be used as an absolute dating technique with no Zeta-calibration necessary. However, beyond the initial study of Hasebe et al. (2004), little work has been done to compare results obtained by LA-ICP-MS with those from EDM analysis, and it remains unclear whether the two methods yield equivalent results. We present an extensive dataset of fission track results that were analysed using both LA-ICP-MS and EDM dating. The samples were selected to represent a variety of compositions, with single grain ages ranging from a few million to over a billion years. Both techniques were applied on identical grains, thereby eliminating uncertainties associated with natural variability. The comparison shows that, with a few exceptions, single grain fission track ages from LA-ICP-MS and EDM are concordant within analytical uncertainties and scatter symmetrically around the 1:1 correlation line. Although the relative difference in single grain ages varies significantly in either direction (up to 70%), there are no systematic variations between the two methods suggesting that this variation is simply due to random sampling effects. However, we did find systematic

  15. Iron isotope compositions and origins of pyrites from the Turee Creek Group, Western Australia: the contribution of high-resolution femtosecond Laser Ablation -MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    d'Abzac, F.; Beard, B. L.; Williford, K. H.; Valley, J. W.; Van Kranendonk, M. J.; Johnson, C.

    2013-12-01

    The Paleoproterozoic Great Oxidation Event (GOE) records a transition from an anoxic environment to a O2-bearing atmosphere, but its timing and duration remain unclear. High-spatial-resolution S isotope analyses by SIMS have shown that pyrite grains in the ~2.4Gy diamictites of the Meteorite Bore Member (MBM; Turee Creek Group, Western Australia), deposited during the GOE, contain evidence for a complex depositional and paragenetic history, including microbial sulfate reduction under low atmospheric O2 yet high seawater sulfate concentrations. The pyrites show various morphologies: euhedral, subhedral, anhedral, rounded, and zoned, where low- δ34S rounded cores may have high-δ34S euhedral/subhedral overgrowths [1]. New in-situ Fe isotope data by femtosecond laser ablation (fs-LA) analysis using Multi Collector ICP-MS on 118 pyrite grains within five rock samples previously analyzed for S isotopes documents δ56Fe values between -2.3‰ and +2.3‰. Transitional cherts at the base of the MBM record the highest δ56Fe values, >0.7‰. Within the upper mudstones/sandstones deposits, anhedral, rounded grains and zoned pyrite cores have a wide range of δ56Fe from -2.3‰ to +1.1‰ whereas euhedral grains and grains overgrowths have mainly positive δ56Fe values, up to +1.34‰, spread over narrower ranges in each sample (<1‰). Non-euhedral grains and rounded grain cores of likely detrital origin have highly scattered δ56Fe values, indicating a range of different sources. Although very low δ56Fe values suggest a source of biologically reduced Fe [2], they can be obtained by precipitation of FeS from low-δ56Fe seawater Fe2+ [3], or might reflect a kinetic signature during pyritization of FeS [4]. High-δ56Fe in pyrite overgrowths and authigenic grains likely reflects precipitation from a hydrothermal fluid (δ56Fe~0.0‰) at T>100°C [5, 6], in agreement with [1]. The δ34S gradient of highly negative to positive values from zoned pyrites cores to rims is well

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

    Compared to non-destructive geochemical analyses, LA-ICP-MS consumes ca. 0.1 μm of material per ablation pulse. It is therefore to be expected that the combined analyses of ca. 200 pulses will encounter geochemical and isotopic complexities in all but the most perfect minerals. Experienced LA-ICP-MS analysts spot down-hole complexities and choose signal integration areas accordingly. In U-Pb geochronology, the task of signal integration choice is complex as the analyst wants to avoid areas of common Pb and Pb-loss and separate true (concordant) age complexity. Petrus and Kamber (2012) developed VizualAge as a tool for reducing and visualising, in real time, U-Pb geochronology data obtained by LA-ICP-MS as an add-on for the freely available U-Pb geochronology data reduction scheme of Paton et al. (2010) in Iolite. The most important feature of VizualAge is its ability to display a live concordia diagram, allowing users to inspect the data of a signal on a concordia diagram as the integration area it is being adjusted, thus providing immediate visual feedback regarding discordance, uncertainty, and common lead for different regions of the signal. It can also be used to construct histograms and probability distributions, standard and Tera-Wasserburg style concordia diagrams, as well as 3D U-Th-Pb and total U-Pb concordia diagrams. More recently, Chew et al. (2014) presented a new data reduction scheme (VizualAge_UcomPbine) with much improved common Pb correction functionality. Common Pb is a problem for many U-bearing accessory minerals and an under-appreciated difficulty is the potential presence of (possibly unevenly distributed) common Pb in calibration standards, introducing systematic inaccuracy into entire datasets. One key feature of the new method is that it can correct for variable amounts of common Pb in any U-Pb accessory mineral standard as long as the standard is concordant in the U/Pb (and Th/Pb) systems after common Pb correction. Common Pb correction

  18. Uranium-lead dating of perovskite from the Afrikanda plutonic complex (Kola Peninsula, Russia) using LA-ICP-MS.

    NASA Astrophysics Data System (ADS)

    Reguir, E.; Camacho, A.; Yang, P.; Chakhmouradian, A. R.; Halden, N. M.

    2009-04-01

    Perovskite (CaTiO3) is a common early crystallizing accessory phase in a variety of alkaline rocks, and has been shown to contain enough U and Th for U-Pb dating. U and Pb analysis of perovskite has been primarily carried out using the SHRIMP or ID-TIMS techniques, and the resulting U-Pb dates commonly yield the emplacement age of the host rock. To our knowledge, only one U-Pb study of perovskite has been done using the LA-ICP-MS (Cox and Wilton, 2006). Some of the advantages of this method over the SHRIMP and ID-TIMS techniques include greater speed and lower cost of analysis. In this work, the U-Pb ages of perovskite from the Afrikanda plutonic complex (Russia) were obtained in situ using the LA-ICP-MS. The measured 238U/206Pb and 207Pb/206Pb ratios were corrected for time-dependent mass-bias using the well-calibrated zircon standard GJ-1 (608.5 ± 0.4 Ma; Jackson et al., 2004). On a Tera-Wasserburg diagram (Tera and Wasserburg, 1972) the analyses of perovskite from two magmatic phases (clinopyroxenite and carbonatite) plot in separate clusters. Although the variations in the 238U/206Pb and 207Pb/206Pb ratios within each group are small, there is enough dispersion between the two clusters to obtain a reasonably precise age of 375 ± 13 Ma (2; MSWD = 0.23), which strongly suggests that the carbonatitic rocks are broadly coeval with the clinopyroxenite. The only other isotopic study on the Afrikanda Complex was done on a clinopyroxenite using the Rb-Sr method and yielded a whole rock-mineral (perovskite, biotite, augite and apatite) isochron age of 364.0 ± 3.1 Ma (2; MSWD = 0.72). This age is within error of our U-Pb date, which demonstrates that LA-ICP-MS-based U-Pb dating of perovskite can serve as a reliable geochronological tool. References Cox, R.A. and Wilton, D.H.C. (2006) U-Pb dating of perovskite by LA-ICP-MS: An example from the Oka carbonatite, Quebec, Canada. Chem. Geol., 235, 21-32. Jackson, S.E., Pearson, N.J., Griffin, W.L. and Belousova, E.A. (2004

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

    PubMed

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

    2016-03-10

    The sulfur isotope is an important geochemical tracer in diverse fields of geosciences. In this study, the effects of three different cone combinations with the addition of N2 on the performance of in situ S isotope analyses were investigated in detail. The signal intensities of S isotopes were improved by a factor of 2.3 and 3.6 using the X skimmer cone combined with the standard sample cone or the Jet sample cone, respectively, compared with the standard arrangement (H skimmer cone combined with the standard sample cone). This signal enhancement is important for the improvement of the precision and accuracy of in situ S isotope analysis at high spatial resolution. Different cone combinations have a significant effect on the mass bias and mass bias stability for S isotopes. Poor precisions of S isotope ratios were obtained using the Jet and X cones combination at their corresponding optimum makeup gas flow when using Ar plasma only. The addition of 4-8 ml min(-1) nitrogen to the central gas flow in laser ablation MC-ICP-MS was found to significantly enlarge the mass bias stability zone at their corresponding optimum makeup gas flow in these three different cone combinations. The polyatomic interferences of OO, SH, OOH were also significantly reduced, and the interference free plateaus of sulfur isotopes became broader and flatter in the nitrogen mode (N2 = 4 ml min(-1)). However, the signal intensity of S was not increased by the addition of nitrogen in this study. The laser fluence and ablation mode had significant effects on sulfur isotope fractionation during the analysis of sulfides and elemental sulfur by laser ablation MC-ICP-MS. The matrix effect among different sulfides and elemental sulfur was observed, but could be significantly reduced by line scan ablation in preference to single spot ablation under the optimized fluence. It is recommended that the d90 values of the particles in pressed powder pellets for accurate and precise S isotope analysis

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

    PubMed

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

    2016-03-10

    The sulfur isotope is an important geochemical tracer in diverse fields of geosciences. In this study, the effects of three different cone combinations with the addition of N2 on the performance of in situ S isotope analyses were investigated in detail. The signal intensities of S isotopes were improved by a factor of 2.3 and 3.6 using the X skimmer cone combined with the standard sample cone or the Jet sample cone, respectively, compared with the standard arrangement (H skimmer cone combined with the standard sample cone). This signal enhancement is important for the improvement of the precision and accuracy of in situ S isotope analysis at high spatial resolution. Different cone combinations have a significant effect on the mass bias and mass bias stability for S isotopes. Poor precisions of S isotope ratios were obtained using the Jet and X cones combination at their corresponding optimum makeup gas flow when using Ar plasma only. The addition of 4-8 ml min(-1) nitrogen to the central gas flow in laser ablation MC-ICP-MS was found to significantly enlarge the mass bias stability zone at their corresponding optimum makeup gas flow in these three different cone combinations. The polyatomic interferences of OO, SH, OOH were also significantly reduced, and the interference free plateaus of sulfur isotopes became broader and flatter in the nitrogen mode (N2 = 4 ml min(-1)). However, the signal intensity of S was not increased by the addition of nitrogen in this study. The laser fluence and ablation mode had significant effects on sulfur isotope fractionation during the analysis of sulfides and elemental sulfur by laser ablation MC-ICP-MS. The matrix effect among different sulfides and elemental sulfur was observed, but could be significantly reduced by line scan ablation in preference to single spot ablation under the optimized fluence. It is recommended that the d90 values of the particles in pressed powder pellets for accurate and precise S isotope analysis

  1. Combined application of a laser ablation-ICP-MS assay for screening and ESI-FTICR-MS for identification of a Cd-binding protein in Spinacia oleracea L. after exposure to Cd.

    PubMed

    Polatajko, Aleksandra; Feldmann, Ingo; Hayen, Heiko; Jakubowski, Norbert

    2011-10-01

    We have studied the binding of the toxic element Cd to plant proteins and have used for this purpose spinach (Spinacia oleracea L.) plants treated with 50 μM Cd(II) as a model system. Laser ablation ICP-MS has been applied for the screening of Cd-binding proteins after separation by native anodal polyacrylamide gel electrophoresis (AN-PAGE) and electroblotting onto membranes. The main Cd-carrying protein band was isolated and investigated by nano-electrospray ionization-Fourier transform ion cyclotron resonance (FTICR) mass spectrometry after tryptic digestion. By this procedure, the main Cd-binding protein was identified as ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO). The latter enzyme has been discussed in the literature to be affected in its activity by oxidative stress induced by Cd. However, in this paper it is demonstrated for the first time that RuBisCO directly binds Cd and thus may be directly altered by this toxic element. A commercially available protein standard was used to verify direct binding of Cd(II) to the protein, even without metabolisation. The resulting metal-protein complex was shown to be stable enough to survive AN-PAGE separation and electroblotting. By the use of size exclusion chromatography coupled with ICP-MS it was demonstrated that the RuBisCO protein standard shows similar metal binding properties to Cd. Furthermore, essential elements such as Mn(II), Fe(II) and Cu(II), which are known to possibly replace the RuBisCO activator Mg(II), were investigated in addition to Zn(II). Again, similar binding properties in comparison to the plant protein were observed.

  2. Role of Sulfur Vapor on PGE-Fractionation Processes in Cu-Ni Deposits: Experimental Study by ICP-MS Laser Ablation

    NASA Astrophysics Data System (ADS)

    Peregoedova, A.; Barnes, S.; Baker, D. R.

    2004-05-01

    We have investigated the transport of platinum-group elements (PGE) and base-metals (BM) by S-vapor in the systems Fe-S-PGE and Fe-Ni-Cu-PGE-S at 1 atm pressure, 1000° C and 1100° C. Open-system, with respect to the gas-phase, conditions were set up using the tube-in-tube technique. A S-rich donor, (Fe,Ni,Cu)1-xS of variable BM ratio, was doped with 2000 ppm of each PGE. A S-poor pyrrhotite (Po) was used as the PGE receiver. The metal/S ratio of the system was varied by changing the donor/receiver ratio to assess whether the metals were transported as S-species or metals. In the system Fe-S-PGE the run products were receiver Po and donor Po containing exsolutions of individual PGE phases (PGM). In the system Fe-Cu-Ni-S-PGE the run products were receiver Po and a donor association composed of monosulfide solid-solution ± Cu-rich sulfide melt ± PGM. The final compositions of both PGE receivers and donors were determined by electron microprobe at McGill University for the major PGE, BM and S, and by ICP-MS-LA at the University of Quebec in Chicoutimi for trace PGE. The detection limit for all PGE is in the 10 to 30 ppb range. The receiver Po contained significant quantities of transported Pt and Pd (PPGE), Os and Au, but little Ir, Ru and Rh (IPGE). In addition, a much higher quantity of Ni was transported trough the vapor-phase (700 ppm to 11300 ppm) compared to Cu (1000 ppm). There is a dependence of the amount of Ni and PPGE transported on the metal/S ratio of the system. This suggests that Ni and the PPGE were transported as BM sulfide species whereas Cu and the IPGE were transported as metals. In experiments where no Cu-rich sulfide liquid formed, Pt (12-38 ppm) was slightly better transported than Pd (7-27 ppm), while in the presence of a sulfide liquid Pd (48-69 ppm) appears to be more effectively transported than Pt (31-44 ppm). In most natural examples where mobilization of PGE has been suggested, the remobilized material is enriched in Cu, Pd and to a

  3. Development of a non-denaturing 2D gel electrophoresis protocol for screening in vivo uranium-protein targets in Procambarus clarkii with laser ablation ICP MS followed by protein identification by HPLC-Orbitrap MS.

    PubMed

    Xu, Ming; Frelon, Sandrine; Simon, Olivier; Lobinski, Ryszard; Mounicou, Sandra

    2014-10-01

    Limited knowledge about in vivo non-covalent uranium (U)-protein complexes is largely due to the lack of appropriate analytical methodology. Here, a method for screening and identifying the molecular targets of U was developed. The approach was based on non-denaturing 1D and 2D gel electrophoresis (ND-PAGE and ND-2D-PAGE (using ND-IEF as first dimension previously described)) in conjunction with laser ablation inductively coupled plasma mass spectrometry (LA-ICP MS) for the detection of U-containing proteins. The proteins were then identified by µbore HPLC-Orbitrap MS/MS. The method was applied to the analysis of cytosol of hepatopancreas (HP) of a model U-bioaccumulating organism (Procambarus clarkii). The imaging of uranium in 2D gels revealed the presence of 11 U-containing protein spots. Six protein candidates (i.e. ferritin, glyceraldehyde-3-phosphate dehydrogenase, triosephosphate isomerase, cytosolic manganese superoxide dismutase (Mn-SOD), glutathione S transferase D1 and H3 histone family protein) were then identified by matching with the data base of crustacea Decapoda species (e.g. crayfish). Among them, ferritin was the most important one. This strategy is expected to provide an insight into U toxicology and metabolism. PMID:25059147

  4. LIBS and LA-ICP-MS; Old techniques, new approaches

    NASA Astrophysics Data System (ADS)

    Mueller, P. A.; Foster, D. A.; Gonzalez, J.; Colucci, M.; Russo, R.

    2012-12-01

    Over the past decade laser ablation in-situ solid sampling for chemical analysis with an ICP-MS analyzer (LA-ICP-MS, single and multi-collector) has become a generally accepted technique across a wide range of disciplines (geochemistry, forensic science, life sciences, etc). More recently, Laser Induced Breakdown Spectrometry (LIBS) has developed into a complementary technique that offers full spectral analysis of the laser plasma without the need for a mass spectrometer. Both techniques provide in-situ solid sample elemental and isotopic analysis at high spatial resolution (<5 microns) with minimal sample preparation. LA-ICP-MS affords the analyst low detection limits (ppb) and the ability to optimize across a specific mass range for high precision element or isotope ratios. LIBS, while providing slightly higher detection limits (ppm), allows for simultaneous and near complete spectral coverage of the laser plasma. Both techniques are capable of producing semi-quantitative and quantitative data. Integration of a LA and LIBS system could be a powerful tool to allow full spectral element and isotope/element ratio data on the same laser plume (plasma and particulates). Although LIBS and LA typically operate under different conditions of pulse length, spot size, and energy, the ability to capture elemental abundance information from the light that is otherwise wasted during LA makes an important complement to the limited number of ions measured in multi-collector ICP-MS analyses. Such an approach would not require the compromises in sampled volume associated with either split-streams (two ICP-MS systems required; diluted aerosol streams) or with peak switching in the MS (magnetic or electrostatic) because extraction of light-based information does not impact the number of ions measured for isotope ratios. We present LIBS experiments with UV-nanosecond lasers at 17mJ energies delivered to spot sizes of <100 μm and light directed to an ICCD detection system on NIST

  5. High resolution analysis of uranium and thorium concentration as well as U-series isotope distributions in a Neanderthal tooth from Payre (Ardèche, France) using laser ablation ICP-MS

    NASA Astrophysics Data System (ADS)

    Grün, Rainer; Aubert, Maxime; Joannes-Boyau, Renaud; Moncel, Marie-Hélène

    2008-11-01

    We have mapped U ( 238U) and Th ( 232Th) elemental concentrations as well as U-series isotope distributions in a Neanderthal tooth from the Middle Palaeolithic site of Payre using laser ablation ICP-MS. The U-concentrations in an enamel section varied between 1 and 1500 ppb. The U-concentration maps show that U-migration through the external enamel surface is minute, the bulk of the uranium having migrated internally via the dentine into the enamel. The uranium migration and uptake is critically dependent on the mineralogical structure of the enamel. Increased U-concentrations are observed along lineaments, some of which are associated with cracks, and others may be related to intra-prismatic zones or structural weaknesses reaching from the dentine into the enamel. The uranium concentrations in the dentine vary between about 25,000 and 45,000 ppb. Our systematic mapping of U-concentration and U-series isotopes provides insight into the time domain of U-accumulation. Most of the uranium was accumulated in an early stage of burial, with some much later overprints. None of the uranium concentration and U-series profiles across the root of the tooth complied with a single stage diffusion-adsorption (D-A) model that is used for quality control in U-series dating of bones and teeth. Nevertheless, in the domains that yielded the oldest apparent U-series age estimates, U-leaching could be excluded. This means that the oldest apparent U-series ages of around 200 ka represent a minimum age for this Neanderthal specimen. This is in good agreement with independent age assessments (200-230 ka) for the archaeological layer, in which it was found. The Th elemental concentrations in the dental tissues were generally low (between about 1 and 20 ppb), and show little relationship with the nature of the tissue.

  6. Using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to explore geochemical taphonomy of vertebrate fossils in the upper cretaceous two medicine and Judith River formations of Montana

    USGS Publications Warehouse

    Rogers, R.R.; Fricke, H.C.; Addona, V.; Canavan, R.R.; Dwyer, C.N.; Harwood, C.L.; Koenig, A.E.; Murray, R.; Thole, J.T.; Williams, J.

    2010-01-01

    Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to determine rare earth element (REE) content of 76 fossil bones collected from the Upper Cretaceous (Campanian) Two Medicine (TMF) and Judith River (JRF) Formations of Montana. REE content is distinctive at the formation scale, with TMF samples exhibiting generally higher overall REE content and greater variability in REE enrichment than JRF samples. Moreover, JRF bones exhibit relative enrichment in heavy REE, whereas TMF bones span heavy and light enrichment fields in roughly equal proportions. TMF bones are also characterized by more negative Ce anomalies and greater U enrichment than JRF bones, which is consistent with more oxidizing diagenetic conditions in the TMF. Bonebeds in both formations show general consistency in REE content, with no indication of spatial or temporal mixing within sites. Previous studies, however, suggest that the bonebeds in question are attritional assemblages that accumulated over considerable time spans. The absence of geochemical evidence for mixing is consistent with diagenesis transpiring in settings that remained chemically and hydrologically stable during recrystallization. Lithology-related patterns in REE content were also compared, and TMF bones recovered from fluvial sandstones show relative enrichment in heavy REE when compared with bones recovered from fine-grained floodplain deposits. In contrast, JRF bones, regardless of lithologic context (sandstone versus mudstone), exhibit similar patterns of REE uptake. This result is consistent with previous reconstructions that suggest that channel-hosted microfossil bonebeds of the JRF developed via the reworking of preexisting concentrations embedded in the interfluve. Geochemical data further indicate that reworked elements were potentially delivered to channels in a recrystallized condition, which is consistent with rapid adsorption of REE postmortem. Copyright ?? 2010, SEPM (Society for

  7. Detrital zircon LASS-ICP-MS petrochronologic depth profiling for determining source-to-sink relationships in the Central Alps.

    NASA Astrophysics Data System (ADS)

    Anfinson, O. A.; Stockli, D. F.; Stockli, L.; Malusa', M. G.

    2015-12-01

    Laser Ablation-Split Stream Depth Profiling (LASS-DP) ICP-MS petrochronology of detrital zircon (DZ) from Oligocene-Miocene strata in the Molasse and Northern Apennines showcases, in the light of the well-constrained depositional history of these successions, the advantages of this novel approach compared to traditional single and split-stream detrital zircon techniques in elucidating sediment provenance and source-to-sink relationships. While DZ U-Pb data from Oligocene-Miocene strata deposited in both the Molasse and Northern Apennines document shifts in the relative abundance of Cadomian, Caledonian, Variscan and Alpine aged detrital zircon, the source regions remain ambiguous due to non-diagnostic crystallization ages, leading to minimal zircon age variability. In contrast, DZ LASS-DP-ICP-MS petrochronology allows for the simultaneous recovery of multiple U-Pb ages and corresponding geochemical data, and thus dramatically increases our ability to resolve the petrogenetic history of individual DZ grains. The technique shows the immense power of determining the growth history of single DZ grains (rim to core relationships) and identifying/resolving the presence and age of thin magmatic/metamorphic overgrowths. Rupelian turbidites in the Apenninic foredeep exhibit a DZ population with consistent <5 mm Cretaceous metamorphic overgrowths that would likely not be resolved as a coherent population in polished sections. LASS-DP ICP-MS analysis of Caledonian and Variscan detrital zircon populations from the Molasse Basin show a distinct shift in rim-core age pairs in individual zircons that point to the erosion of different source during progressive Alpine unroofing. The geochemical data confirm a crustally derived magmatic source for the majority of the detrital zircon grains within the basin. While this technique, in comparison to traditional polished mounts, might underrepresent older core ages, this slight bias is clearly offset by the better definition and

  8. Gold in the Brunswick No. 12 volcanogenic massive sulfide deposit, Bathurst Mining Camp, Canada: Evidence from bulk ore analysis and laser ablation ICP-MS data on sulfide phases

    NASA Astrophysics Data System (ADS)

    McClenaghan, Sean H.; Lentz, David R.; Martin, Jillian; Diegor, Wilfredo G.

    2009-07-01

    The 329-Mt Brunswick No. 12 volcanogenic massive sulfide deposit (total resource of 163 Mt at 10.4% Zn, 4.2% Pb, 0.34% Cu, and 115 g/t Ag) is hosted within a Middle Ordovician bimodal volcanic and sedimentary sequence. Massive sulfides are for the most part syngenetic, and the bulk of the sulfide ore occurs as a Zn-Pb-rich banded sulfide facies that forms an intimate relationship with a laterally extensive Algoma-type iron formation and defines the Brunswick Horizon. Zone refining of stratiform sulfides is considered to have resulted in the development of a large replacement-style Cu-rich basal sulfide facies, which is generally confined between the banded sulfide facies and an underlying stringer sulfide zone. Complex polyphase deformation and associated lower- to upper-greenschist facies regional metamorphism is responsible for the present geometry of the deposit. Textural modification has resulted in a general increase in grain size through the development of pyrite and arsenopyrite porphyroblasts, which tend to overprint primary mineral assemblages. Despite the heterogeneous ductile deformation, primary features have locally been preserved, such as fine-grained colloform pyrite and base and precious metal zonation within the Main Zone. Base metal and trace element abundances in massive sulfides from the Brunswick No. 12 deposit indicate two distinct geochemical associations. The basal sulfide facies, characterized by a proximal high-temperature hydrothermal signature (Cu-Co-Bi-Se), contains generally low Au contents averaging 0.39 ppm ( n = 34). Conversely, Au is enriched in the banded sulfide facies, averaging 1.1 ppm Au ( n = 21), and is associated with an exhalative suite of elements (Zn-Pb-As-Sb-Ag-Sn). Finely laminated sulfide lenses hosted by iron formation at the north end of the Main Zone are further enriched in Au, averaging 1.7 ppm ( n = 41) and ranging up to 8.2 ppm. Laser ablation inductively coupled plasma-mass spectrometry (ICP-MS) analyses of

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

    PubMed

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

    2011-12-01

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

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

    NASA Astrophysics Data System (ADS)

    Xu, Gu-feng; Wang, Hong-mei

    2001-08-01

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

  11. Magmatic Activity and Crustal Melting During Orogenesis: Laser-ablation U-Pb Geochronology of Dike and Leucosome Generations in Granulites of the Gruf Complex, Central Alps

    NASA Astrophysics Data System (ADS)

    Savage, J. A.; Oalmann, J.; Bousquet, R.; Moeller, A.

    2012-12-01

    Magmatic leucosomes and dikes in metamorphic terranes provide an opportunity to correlate accessory phase crystallization ages with the timing of deformation and metamorphic events, as well as larger scale magmatic intrusions. The Gruf Complex consists of upper amphibolite to lower granulite facies migmatitic gneisses and scarce, UHT sapphirine granulites and is bordered by the c. 31 Ma tonalite-granodiorite Bergell Intrusion and the c. 24 Ma Novate S-type leucogranite. Several mineralogically distinct types of leucosomes and dikes have been identified: 1) biotite-bearing leucosomes, which define the main foliation and are commonly folded; 2) hornblende- and biotite-bearing dikes, which are either boudinaged or crosscut the main foliation; 3) pegmatitic muscovite-, garnet-, beryll-bearing dikes, which commonly crosscut all other rock types. These field observations indicate a change in melt composition during and after the regional metamorphic event and its associated deformation. To correlate these melt types with the timing of metamorphism of the Gruf Complex, and the Bergell and Novate intrusions, U-Pb zircon ages were obtained from several dike and leucosome samples. Grains were separated, mounted in epoxy, and imaged by cathodoluminescence prior to U-Pb isotope analysis by LA-ICP-MS. The outermost zircon growth zones were targeted in order to determine the crystallization age of the host magma. All of the analyzed samples contain oscillatory-zoned domains with ages between 250 Ma and 300 Ma. A leucosome sample from within a brecciated metaperidotite enclave in the granulites contains equant, sector-zoned "soccer ball" zircon grains with an age of 32.4±1.0 Ma. Most dike samples contain unzoned or sector-zoned rims or mantles that range from 30-33 Ma. Most of the pegmatitic samples, regardless of their degree of deformation, contain zircon crystals with weakly zoned rims ranging from 24-27 Ma. However, some undeformed pegmatitic samples lack zircon domains

  12. ICP-MS Data Analysis Software

    1999-01-14

    VG2Xl - this program reads binary data files generated by VG instrumentals inductively coupled plasma-mass spectrometers using PlasmaQuad Software Version 4.2.1 and 4.2.2 running under IBM OS/2. ICPCalc - this module is a macro for Microsoft Excel written in VBA (Virtual Basic for Applications) that performs data analysis for ICP-MS data required for nuclear materials that cannot readily be done with the vendor''s software. VG2GRAMS - This program reads binary data files generated by VGmore » instruments inductively coupled plasma mass spectrometers using PlasmaQuad software versions 4.2.1 and 4.2.2 running under IBM OS/2.« less

  13. Elemental Analysis and Comparison of Bulk Soil Using LA-ICP-MS and LIBS methods

    NASA Astrophysics Data System (ADS)

    Almirall, J.

    2012-04-01

    Elemental analysis methods utilizing Laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS) were developed and used in the characterization of soil samples from the US and Canada as part of a comprehensive forensic evaluation of soils. A LA-ICP-MS method was recently optimized for analysis and comparison between different soil samples in an environmental forensic application [1,2] and LIBS has recently attracted the interest of analytical chemists and forensic laboratories as a simpler, lower cost alternative to the more established analytical methods. In developing a LIBS method, there are many parameters to consider, including laser wavelength, spectral resolution, sensitivity, and matrix effects. The first LIBS method using a 266 nm laser for forensic soil analysis has also been recently reported by our group [3]. The results of an inter-laboratory comparison involving thirteen (13) laboratories conducting bulk elemental analysis by various methods are also reported. The aims of the inter-laboratory tests were: a) to evaluate the inter-laboratory performance of three methods (LA-ICP-MS, µXRF and LIBS) in terms of accuracy (bias), precision (relative standard deviation, RSD) and sensitivity using standard reference materials (SRMs); b) to evaluate the newly released NIST SRM 2710a, which supersedes 2710; and c) to evaluate the utility of LIBS as an alternative technique to LA-ICP-MS and µXRF for bulk analysis of soils. Each sample and standard was homogenized in a high-speed ball mill and pressed into pellets. Participants were instructed to measure the following elements: 7Li, 25Mg, 27Al, 42Ca, 45Sc, 47,49Ti, 51V, 55Mn, 88Sr, 137Ba, 206,207,208 Pb (LA-ICP-MS); Ti, Cr, Mn, Fe, Cu, Sr, Zr, Pb (µXRF); Ba, Cr, Cu, Fe, Li, Mg, Mn, Pb, Sr, Ti, Zr (LIBS). For both LIBS and µXRF, the choice of appropriate spectral lines was determined by the user, optimizing for linearity, sensitivity and precision

  14. Tubular textures in pillow lavas from a Caledonian west Norwegian ophiolite: A combined TEM, LA-ICP-MS, and STXM study

    NASA Astrophysics Data System (ADS)

    Fliegel, Daniel; Wirth, Richard; Simonetti, Antonio; Schreiber, Anja; Furnes, Harald; Muehlenbachs, Karlis

    2011-02-01

    Tubular alteration textures, mineralized by titanite, in glassy rims of pillow lavas from a Norwegian ophiolite (Solund-Stavfjord ophiolite complex (SSOC)) are described and characterized by a multimethod approach. Tubular alteration textures, mineralized by titanite, have been previously proposed to result from bioalteration. The microstructure of the titanite and the tubes is investigated using focused ion beam milling in combination with transmission electron microscopy (TEM) and scanning transmission X-ray microscopy (STXM). These indicate an assemblage of submicrometer-sized (about 500 nm) titanite single crystals with no organic film or residue in between the grains. In situ U-Pb radiometric dating of the titanite, using laser ablation-multicollector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS), yielded a metamorphic age of 442 ± 13 Ma. An isotope dilution-thermal ionization mass spectrometric age obtained previously for zircons from the SSOC plutonic rocks yielded a magmatic age of 443 ± 3 Ma. The overlap in ages indicates that subseafloor metamorphism, responsible for titanite formation, occurred during seafloor or subseafloor formation of the tubular alteration textures. The rare earth element contents of the titanite were determined using LA-ICP-MS and chondrite-normalized patterns are similar to those of the SSOC volcanics; hence these do not reflect hydrothermal or seawater influence. The Y/Ho ratio of ˜20-30 in the titanite is also consistent with an upper mantle-derived origin. The sum of all of the spatial resolved data reported here neither supports nor refutes a biogenic origin for the tubular textures.

  15. Laser Ablation Split Stream (LASS) U-Pb & Lu-Hf Isotope Analysis of Detrital Zircons from the Old Red Sandstone, NW Svalbard: Implications for Northern Caledonian Paleogeography

    NASA Astrophysics Data System (ADS)

    Beranek, L. P.; Gee, D. G.; Fisher, C. M.

    2015-12-01

    The Svalbard archipelago consists of three Caledonian provinces that were assembled by thrusting and transcurrent faulting during the Silurian and Devonian in a location directly northeast of the Greenland Caledonides. Syn- to post-orogenic alluvial strata, referred to as the Old Red Sandstones, filled pull-apart basins adjacent to the transcurrent faults and comprise cover assemblages that help constrain the timing of the Caledonian orogeny. To further investigate the tectonic history and paleogeography of the Raudfjorden-Liefdefjorden-Woodfjorden area of Spitsbergen, NW Svalbard, we analyzed rock samples of the Old Red Sandstones and underlying Precambrian basement complexes for detrital zircon analysis. Laboratory studies of the Old Red Sandstones include the novel Laser Ablation Split Stream (LASS) technique, which allows for simultaneous U-Pb & Lu-Hf isotope analysis of zircon crystals. Lower Devonian Red Bay Group strata contain a range of early Neoproterozoic to Neoarchean detrital zircons with prominent age peaks c. 960, 1050, 1370, 1450, 1650, and 2700 Ma; subordinate Ordovician (c. 460-490 Ma) and Cryogenian (c. 650 Ma) detrital zircons occur in a subset of the samples. Underlying Precambrian metasedimentary rocks are composed of similar earliest Neoproterozoic to Neoarchean age populations, which argues for much of the Red Bay Group to be derived from local basement rocks during thrusting and other faulting. The U-Pb ages and Hf isotope compositions of Paleozoic to Neoarchean detrital zircons are consistent with Arctic crustal evolution, and support the hypothesis that northwestern and northeastern provinces of the Svalbard Caledonides are extruded fragments of the northeast Greenland allochthons. The new Hf isotope results further allow paleogeographic and stratigraphic comparisons with rock assemblages proximal to the North Atlantic Caledonides during the Silurian-Devonian, including the Pearya terrane of Ellesmere Island, Alexander terrane of NW

  16. TEMORA 1: A new zircon standard for Phanerozoic U-Pb geochronology

    USGS Publications Warehouse

    Black, L.P.; Kamo, S.L.; Allen, C.M.; Aleinikoff, J.N.; Davis, D.W.; Korsch, R.J.; Foudoulis, C.

    2003-01-01

    The role of the standard is critical to the derivation of reliable U-Pb zircon ages by micro-beam analysis. For maximum reliability, it is critically important that the utilised standard be homogeneous at all scales of analysis. It is equally important that the standard has been precisely and accurately dated by an independent technique. This study reports the emergence of a new zircon standard that meets those criteria, as demonstrated by Sensitive High Resolution Ion MicroProbe (SHRIMP), isotope dilution thermal ionisation mass-spectrometry (IDTIMS) and excimer laser ablation- inductively coupled plasma-mass-spectrometry (ELA-ICP-MS) documentation. The TEMORA 1 zircon standard derives from the Middledale Gabbroic Diorite, a high-level mafic stock within the Palaeozoic Lachlan Orogen of eastern Australia. Its 206Pb/238U IDTIMS age has been determined to be 416.75??0.24 Ma (95% confidence limits), based on measurement errors alone. Spike-calibration uncertainty limits the accuracy to 416.8??1.1 Ma for U-Pb intercomparisons between different laboratories that do not use a common spike. ?? 2003 Published by Elsevier Science B.V. All rights reserved.

  17. Element Distribution in Allende Determined by LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Wombacher, F.; Funk, C.; Frick, D. A.; Koch, J.; Günther, D.

    2016-08-01

    A novel LA-ICP-MS method has been developed in order to evaluate elemental distributions of 26 major and trace elements in chondritic meteorites. A reconnaissance study on a section from the Allende chondrite is presented.

  18. Elemental impurity analysis of mercuric iodide by ICP/MS

    SciTech Connect

    Cross, E.S. . Santa Barbara Operations); Mroz, E.; Olivares, J.A. )

    1993-01-01

    A method has been developed to analyze mercuric iodide (HgI[sub 2]) for elemental contamination using Inductively Coupled Plasma/Mass Spectroscopy (ICP/MS). This paper will discuss the ICP/MS method, the effectiveness of purification schemes for removing impurities from HgI[sub 2], as well as preliminary correlations between HgI[sub 2] detector performance and elemental contamination levels.

  19. Single grain detrital rutile U-Pb chronology: a key provenance tracer

    NASA Astrophysics Data System (ADS)

    Bracciali, Laura; Parrish, Randall R.; Najman, Yani; Horstwood, Matthew S. A.; Condon, Daniel J.

    2013-04-01

    Rutile is an accessory mineral commonly found in the heavy mineral suite of detrital rocks due to its stability during the sedimentary processes. This mineral originates mainly in medium- to high-grade metamorphic and some igneous rocks and similarly to zircon and other U-bearing minerals can be dated by the U-Pb method. Nevertheless, there are still very few applications of U-Pb dating of rutile to provenance studies, likely because it usually has a lower U content compared to zircon (which in turn leads to lower radiogenic Pb content limiting measurement quality) and it can contain a relatively large proportion of common (non radiogenic) Pb. In addition, there is a scarcity of widely available good quality natural rutile reference materials that can be used to assess reproducibility and accuracy of the dating technique. We have addressed these issues and characterized two ~ 1.8 Ga rutile reference materials (namely Sugluk-4 and PCA-S207 from granulite facies belts of the Canadian Shield) by SEM, trace elements, U-Pb ID-TIMS, and intra-grain and inter-grain U-Pb LA-MC-ICP-MS analysis. LA-U-Pb data (n ~ 500 for each of the two reference materials, collected using a New Wave Research 193 nm wavelength laser ablation system coupled to a Nu Plasma HR mass spectrometer) have a reproducibility of 206Pb/238U and 207Pb/206Pb of ~2-4% (at the 2? level), which is only modestly worse than long-term data for multiple zircon standards, this being due to the real variation in measured values arising from limited Pb loss, age variation related to cooling, and common Pb variability. The analytical measurement of rutile U-Pb data is rapid, allows high spatial resolution (the laser sampling protocol employs a 50 or 35 μm static spot) and does not include common Pb correction [1]. We have applied our refined method to constrain provenance of rutile from modern drainages from British Columbia and the eastern Himalaya (with rutile ages as young as 75% of all rutile grains in a

  20. Micro-spatial variations of heavy metals in the teeth of walrus as determined by laser ablation ICP-MS: the potential for reconstructing a history of metal exposure.

    PubMed

    Evans, R D; Richner, P; Outridge, P M

    1995-01-01

    This study explored the possibility of using laser ablation inductively-coupled plasma-mass spectroscopy to measure trace metals and other elements within the annual growth layers of the teeth of walrus harvested from the Canadian Arctic. Using sample ablation "footprints" of 125 microns diameter on transects across the exposed cross-sections of teeth, this technique detected Pb, Cu, Zn and Sr, but not Cd, in tooth cementum. The micro-spatial patterns of elements were consistent among different transects on the same tooth, and revealed subtle differences between animals of different ages. The youngest walrus in the sample (4 yr) contained higher concentrations of Pb and Cu than older animals in the growth layer deposited during the first year of life, while the oldest animal (33 yr) exhibited higher Pb and Zn than younger animals in the outer layer corresponding to the year 1988. The differences between animals and across annual layers may reflect both life history and metal exposure phenomena, including high amounts of metals transferred from mothers to pups in maternal milk. The ability to detect metals in a repeatable fashion within annual growth layers suggests that metal exposure histories accurate to within a year might be re-constructed for the life-times of long-lived animals, and that a series of such individual studies would allow exposure histories covering centuries to be quickly assembled. These data may suggest the most likely explanation for the currently high levels of some metals observed in certain Arctic marine mammals, i.e., natural phenomenon or anthropogenic contamination.

  1. Trace-element study and uranium-lead dating of perovskite from the Afrikanda plutonic complex, Kola Peninsula (Russia) using LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Reguir, Ekaterina P.; Camacho, Alfredo; Yang, Panseok; Chakhmouradian, Anton R.; Kamenetsky, Vadim S.; Halden, Norman M.

    2010-11-01

    The U-Pb geochronology of perovskite is a powerful tool in constraining the emplacement age of silica-undersaturated rocks. The trace-element and U-Pb isotopic compositions of perovskite from clinopyroxenite and silicocarbonatite from the Afrikanda plutonic complex (Kola, Russia) were determined by laser-ablation inductively-coupled mass-spectrometry (LA-ICP-MS). In addition, the Sr isotopic composition of perovskite was measured by isotope-dilution mass-spectrometry to better constrain the relations between its host rocks. Perovskite from the two rock types shows a different degree of enrichment in Na, Mg, Mn, Pb, Fe, Al, V, rare-earth elements, Zr, Hf, Th, U and Ta. The perovskite 87Sr/86Sr values are within analytical uncertainty of one another and fall within the range of mantle values. The 206Pb/238U ages (corrected for common lead using 207Pb-method) of perovskite from silicocarbonatite statistically yield a single population with a weighted mean of 371 ± 8 Ma (2σ; MSWD = 0.071). This age is indistinguishable, within uncertainty, to the clinopyroxenite weighted mean 206Pb/238U age of 374 ± 10 Ma (2σ; MSWD = 0.18). Our data are in good agreement with the previous geochronological study of the Afrikanda complex. The observed variations in trace-element composition of perovskite from silicocarbonatite and clinopyroxenite indicate that these rocks are not related by crystal fractionation. The Sr isotopic ratios and the fact that the two rocks are coeval suggest that they were either produced from a single parental melt by liquid immiscibility, or from two separate magmas derived at different degrees of partial melting from an isotopically equilibrated, but modally complex mantle source.

  2. Allanite from the El Muerto Pegmatite, Oaxaca, Mexico: A Potential New Standard for 232Th-208Pb Dating by LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Price, J.; Crowley, J. L.; Solari, L.; Prol-Ledesma, R.

    2012-12-01

    Allanite dating may be important to studies addressing tectonomagmatic evolution, provenance of monocyclic sediment, and mineral weathering. Obtaining accurate allanite ages by SIMS has been challenging and time-consuming due to the mineral's extreme chemical variability which often prevents finding adequately matrix-matched standards. Isotopic measurements by LA-ICP-MS minimize the need for standards of nearly identical composition to the unknown allanite being analyzed, and it is done relatively rapidly. Dating by LA-ICP-MS requires high quality standards for isotopic fractionation corrections. However, readily accessible and well characterized allanite standards are scarce. We investigated gemstone allanite from the El Muerto pegmatite, Oaxaca, Mexico, as a potential new geochronology standard for 232Th-208Pb allanite dating by LA-ICP-MS. Compositional homogeneity was thoroughly investigated by scanning and backscatter electron microscopy, cathodoluminescence, quantitative and qualitative energy dispersive x-ray spectroscopy, electron microprobe, and LA-ICP-MS. The possibility of metamictization was investigated by extensive X-ray diffraction analyses. The El Muerto allanite was U-Pb dated by ID-TIMS, with common Pb ratios determined from cogenetic K-feldspar by ID-TIMS and LA-MC-ICP-MS. Future work includes Th-Pb dating by ID-TIMS. The samples investigated are homogeneous with respect to major and trace elements. Major element compositional results are generally in agreement with published values, and no metamictization was identified despite the allanite being nearly 1 Ga. The only limitation of the El Muerto allanite is that it contains small, generally <100 μm, scarce inclusions of quartz, calciothorite, albite, calcite, and biotite. However, these grains are easily recognized and avoided during LA-ICP-MS analyses. Based on these results, the El Muerto allanite has the potential to serve as a standard for LA-ICP-MS dating.

  3. Recent advances in quantitative LA-ICP-MS analysis: challenges and solutions in the life sciences and environmental chemistry.

    PubMed

    Limbeck, Andreas; Galler, Patrick; Bonta, Maximilian; Bauer, Gerald; Nischkauer, Winfried; Vanhaecke, Frank

    2015-09-01

    Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is a widely accepted method for direct sampling of solid materials for trace elemental analysis. The number of reported applications is high and the application range is broad; besides geochemistry, LA-ICP-MS is mostly used in environmental chemistry and the life sciences. This review focuses on the application of LA-ICP-MS for quantification of trace elements in environmental, biological, and medical samples. The fundamental problems of LA-ICP-MS, such as sample-dependent ablation behavior and elemental fractionation, can be even more pronounced in environmental and life science applications as a result of the large variety of sample types and conditions. Besides variations in composition, the range of available sample states is highly diverse, including powders (e.g., soil samples, fly ash), hard tissues (e.g., bones, teeth), soft tissues (e.g., plants, tissue thin-cuts), or liquid samples (e.g., whole blood). Within this article, quantification approaches that have been proposed in the past are critically discussed and compared regarding the results obtained in the applications described. Although a large variety of sample types is discussed within this article, the quantification approaches used are similar for many analytical questions and have only been adapted to the specific questions. Nevertheless, none of them has proven to be a universally applicable method.

  4. ICP-MS for multiplex absolute determinations of proteins.

    PubMed

    Sanz-Medel, Alfredo

    2010-11-01

    In the last few years MS-based proteomics has been turning quantitative because only the quantity of existing proteins or changes of their abundance in a studied sample reflect the actual status and the extent of possible changes in a given biological system. So far, however, only relative quantifications are common place. Recently, the ideal analytical features of ICP-MS that allow robust, accurate and precise absolute determinations of heteroelements (present in proteins and their peptides) have opened the door to its use, as a complementary ion source of MALDI- and/or ESI-(MS), in achieving the "absolute" quantification of a protein. Unfortunately, so far such "heteroatom-tagged proteomics" applications deal with only single-heteroatom measurements. Thus, the outstanding capability of ICP-MS for multi-element (-isotope) simultaneous determinations is somewhat wasted. On the other hand, multiplexed determinations of proteins (e.g. in common or new multiplexed formats) today constitute a pressing need in medical science (e.g. to determine accurately many biomarkers at a time). This is a clear trend in analytical science where ICP-MS could eventually play an important role. Therefore, reported approaches to multiplex protein determinations using ICP-MS, with liquid sample nebulisation and with laser direct sampling from a solid, are discussed here. Apart from such multiplex bioassays for absolute protein determinations, efforts to simultaneously quantitate enzyme activities are also discussed. It appears that the time is ripe to combine the multi-isotopic character of ICP-MS with well-known multi-analyte separation techniques (e.g. HPLC or multiplex immunoassays) to tackle the challenge of analysing abundances and activities of several proteins and enzymes, respectively, in a single assay. Many attractive opportunities for creative work and interdisciplinary developments for analytical atomic spectroscopists seem to lie ahead related to multiplexed quantitative

  5. A table of polyatomic interferences in ICP-MS

    USGS Publications Warehouse

    May, Thomas W.; Wiedmeyer, Ray H.

    1998-01-01

    Spectroscopic interferences are probably the largest class of interferences in ICP-MS and are caused by atomic or molecular ions that have the same mass-to-charge as analytes of interest. Current ICP-MS instrumental software corrects for all known atomic “isobaric” interferences, or those caused by overlapping isotopes of different elements, but does not correct for most polyatomic interferences. Such interferences are caused by polyatomic ions that are formed from precursors having numerous sources, such as the sample matrix, reagents used for preparation, plasma gases, and entrained atmospheric gases.

  6. Isotopic analyses by ICP-MS in clinical samples.

    PubMed

    Rodushkin, Ilia; Engström, Emma; Baxter, Douglas C

    2013-03-01

    This critical review focuses on inductively coupled plasma mass spectrometry (ICP-MS) based applications for isotope abundance ratio measurements in various clinical samples relevant to monitoring occupational or environmental exposure, human provenancing and reconstruction of migration pathways as well as metabolic research. It starts with a brief overview of recent advances in ICP-MS instrumentation, followed by selected examples that cover the fields of accurate analyte quantification using isotope dilution, tracer studies in nutrition and toxicology, and areas relying upon natural or man-made variations in isotope abundance ratios (Pb, Sr, actinides and stable heavy elements). Finally, some suggestions on future developments in the field are provided.

  7. Optimization of laser ablation and signal enhancement for nuclear material detection

    NASA Astrophysics Data System (ADS)

    LaHaye, Nicole L.

    The purpose of the study was to investigate the role of different laser parameters on laser ablation properties, specifically in terms of performance in laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Many laser parameters affect laser ablation performance, including laser wavelength and pulse duration, as presented here. It was previously thought that wavelength plays no role in ultrafast laser ablation; however, it was found that shorter wavelength yields lower detection limits and ablation threshold. Our results also demonstrate that in the laser pulse duration range of 40 fs to 1 ps, negligible differences occur in signal intensity, elemental ratios, and detection limits. U/Pb and U/Th ratios, which were examined to ensure limited fractionation, give comparable results at all pulse widths investigated. A parametric study of plasma hydrodynamics will also be presented. An elemental detection method combining laser induced breakdown spectroscopy (LIBS) and LA-ICP-MS is developed, with plasma density and temperature actively monitored to investigate how plasma conditions affect ICP-MS results. The combination of these two methods will help to mitigate the disadvantages of using each technique individually. Depth and spatial analysis of thin films was performed using femtosecond LA-ICP-MS to study the stoichiometric distribution of the films. The thin film-substrate interface was probed, revealing intermixing between the two layers. Lastly, the persistence of uranium emission in laser-produced plasmas (LPP) was investigated under various Ar ambient environments. Plasma collisional effects and confinement play a very important role in emission intensity and persistence, yielding important results for future LIBS and laser absorption spectroscopy (LAS) research. Lastly, suggestions for future work are made, which include extension of the LIBS and LA-ICP-MS systems to other samples like oxide thin films and spatial and depth profiling of known

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  9. Online Standard Additions Technique for La-ICP-MS Using a Desolvating Nebulizer System

    NASA Astrophysics Data System (ADS)

    Roy, J.; Asogan, D.; Moody, S.; Clarke, D.

    2014-12-01

    Historically, quantification with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been limited to the ability to matrix match both standards and samples. This can prove problematic when a particular matrix matched standard is not readily available. Liquid standard addition has been shown1-4 as an alternative technique for quantification that does not require matrix matching; however, further fundamental study is needed especially considering the different mass flow rates delivered to the plasma from traditional pneumatic nebulizers and laser ablation itself. In this work, the authors combine a specialized low-flow desolvating nebulizer system with LA-ICP-MS. This nebulizer system efficiently removes water vapour, thereby significantly reducing oxide based mass spectral interferences. For the instrument setup, the output from the laser is combined with the dried aerosol from the nebulizer system prior to entering the ICP-MS source. By using two sources of dry aerosol, mixing efficiency is improved whilst minimising plasma power lost to solvent (water vapour) processing. The method was applied to both USGS Green River Shale and an Arkansas Womble Shale. The results showed a number of elements that were correctly quantified using the technique as compared to reference values. References Gunther, D., Cousin, H., Magyar, B., Leopold, I., J. Anal. Atom. Spectrom., 1997, 12, 165 - 170. Leach, J.J., Allen, L. A., Aeschliman, D.B., Houk, R.S., Anal. Chem., 1999, 71, 440 - 445. O'Conner, C.J.P., Sharp, B.L, Evans, P.J., Anal. Atom. Spectrom., 2006, 21, 556. Yang, C.K., Chi, P.H., Lin, Y.C., Sun, Y.C., Yang, M.H., Talanta, 2010, 80, 1222 - 1227.

  10. LA-ICP-MS of rare earth elements concentrated in cation-exchange resin particles for origin attribution of uranium ore concentrate.

    PubMed

    Asai, Shiho; Limbeck, Andreas

    2015-04-01

    Rare earth elements (REE) concentrated on cation-exchange resin particles were measured with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to obtain chondrite-normalized REE plots. The sensitivity of REE increased in ascending order of the atomic number, according to the sensitivity trend in pneumatic nebulization ICP-MS (PN-ICP-MS). The signal intensities of REE were nearly proportional to the concentrations of REE in the immersion solution used for particle-preparation. Minimum measurable concentration calculated from the net signals of REE was approximately 1 ng/g corresponding to 0.1 ng in the particle-preparation solution. In LA analysis, formation of oxide and hydroxide of the light REE and Ba which causes spectral interferences in the heavy REE measurement was effectively attenuated due to the solvent-free measurement capability, compared to conventional PN-ICP-MS. To evaluate the applicability of the proposed method, the REE-adsorbed particles prepared by immersing them in a U-bearing solution (commercially available U standard solution) were measured with LA-ICP-MS. Aside from the LA analysis, each concentration of REE in the same U standard solution was determined with conventional PN-ICP-MS after separating REE by cation-exchange chromatography. The concentrations of REE were ranging from 0.04 (Pr) to 1.08 (Dy) μg/g-U. The chondrite-normalized plot obtained through LA-ICP-MS analysis of the U standard sample exhibited close agreement with that obtained through the PN-ICP-MS of the REE-separated solution within the uncertainties.

  11. Elemental impurity analysis of mercuric iodide by ICP/MS

    SciTech Connect

    Cross, E.S.; Mroz, E.; Olivares, J.A.

    1994-06-01

    A method has been developed to analyze mercuric iodide (HgI{sub 2}) for elemental contamination using Inductively Coupled Plasma/Mass Spectroscopy (ICP/MS). This paper discusses the ICP/MS method, the effectiveness of purification schemes for removing impurities from HgI{sub 2}, as well as preliminary correlations between HgI{sub 2} detector performance and elemental contamination levels. The purified HgI{sub 2} is grown into a single crystal by physical vapor transport. The crystal are cut into slices and they are fabricated into room temperature radiation detectors and photocells. Crystals that produce good resolution gamma detector do not necessarily make good resolution photocells or x-ray detectors. Many factors other than elemental impurities may contribute to these differences in performance.

  12. Measuring sulfur isotopes by multicollector ICP-MS

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

    The stable isotopes of sulfur have traditionally been measured by converting analytes to SO2, which is then introduced to a gas-source isotope ratio mass spectrometer (IRMS). Recently, we and several other groups have begun measuring S isotopes using a multicollector inductively-coupled plasma mass spectrometer (MC-ICP-MS). The approach offers several advantages, including decreased reliance on preparatory chemical conversion (including combustion) of analytes, greater flexibility of sample introduction, and increased sensitivity. Sulfur is measured as monoatomic S+ ions produced in the plasma source, and can be introduced in a variety of forms including dissolved sulfate or sulfide, or as organosulfur compounds either in solution or in the gas phase. A primary requirement for accurate measurements is resolving isobaric interferences from O2+, which requires a mass analyzer with resolution > 4000. Using a Thermo Neptune system, we document accuracy and precision for δ34S near the shot-noise limit (ie, counting statistics) for both aqueous solutions and gas streams. For samples containing 50 pmol S (as gaseous SF6), this corresponds to ~0.3%; for 50 nmol S (as aqueous SO4) this is ~0.02%. One important application of this new analytical approach is the measurement of S isotopes in volatile and semivolatile organic compounds. No IRMS-based methods for measuring compound-specific S isotopes currently exist. We have demonstrated this capability by coupling a capillary gas chromatograph (GC) directly to the ICP-MS via a heated transfer line. Isotope ratios (δ34S values) are calculated relative to co-injected peaks of SF6 reference gas, in the same manner as is used by GC-combustion-IRMS approaches. As a demonstration of this capability, we measured the δ34S values of individual thiophene isomers separated by GC from a crude oil, which range over 20% for compounds from the same oil. A second application of ICP-MS to sulfur isotopes is the measurement of dissolved

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  14. External calibration strategy for trace element quantification in botanical samples by LA-ICP-MS using filter paper.

    PubMed

    Nunes, Matheus A G; Voss, Mônica; Corazza, Gabriela; Flores, Erico M M; Dressler, Valderi L

    2016-01-28

    The use of reference solutions dispersed on filter paper discs is proposed for the first time as an external calibration strategy for matrix matching and determination of As, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr, V and Zn in plants by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS). The procedure is based on the use of filter paper discs as support for aqueous reference solutions, which are further evaporated, resulting in solid standards with concentrations up to 250 μg g(-1) of each element. The use of filter paper for calibration is proposed as matrix matched standards due to the similarities of this material with botanical samples, regarding to carbon concentration and its distribution through both matrices. These characteristics allowed the use of (13)C as internal standard (IS) during the analysis by LA-ICP-MS. In this way, parameters as analyte signal normalization with (13)C, carrier gas flow rate, laser energy, spot size, and calibration range were monitored. The calibration procedure using solution deposition on filter paper discs resulted in precision improvement when (13)C was used as IS. The method precision was calculated by the analysis of a certified reference material (CRM) of botanical matrix, considering the RSD obtained for 5 line scans and was lower than 20%. Accuracy of LA-ICP-MS determinations were evaluated by analysis of four CRM pellets of botanical composition, as well as by comparison with results obtained by ICP-MS using solution nebulization after microwave assisted digestion. Plant samples of unknown elemental composition were analyzed by the proposed LA method and good agreement were obtained with results of solution analysis. Limits of detection (LOD) established for LA-ICP-MS were obtained by the ablation of 10 lines on the filter paper disc containing 40 μL of 5% HNO3 (v v(-1)) as calibration blank. Values ranged from 0.05 to 0.81  μg g(-1). Overall, the use of filter paper as support for dried aqueous

  15. External calibration strategy for trace element quantification in botanical samples by LA-ICP-MS using filter paper.

    PubMed

    Nunes, Matheus A G; Voss, Mônica; Corazza, Gabriela; Flores, Erico M M; Dressler, Valderi L

    2016-01-28

    The use of reference solutions dispersed on filter paper discs is proposed for the first time as an external calibration strategy for matrix matching and determination of As, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr, V and Zn in plants by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS). The procedure is based on the use of filter paper discs as support for aqueous reference solutions, which are further evaporated, resulting in solid standards with concentrations up to 250 μg g(-1) of each element. The use of filter paper for calibration is proposed as matrix matched standards due to the similarities of this material with botanical samples, regarding to carbon concentration and its distribution through both matrices. These characteristics allowed the use of (13)C as internal standard (IS) during the analysis by LA-ICP-MS. In this way, parameters as analyte signal normalization with (13)C, carrier gas flow rate, laser energy, spot size, and calibration range were monitored. The calibration procedure using solution deposition on filter paper discs resulted in precision improvement when (13)C was used as IS. The method precision was calculated by the analysis of a certified reference material (CRM) of botanical matrix, considering the RSD obtained for 5 line scans and was lower than 20%. Accuracy of LA-ICP-MS determinations were evaluated by analysis of four CRM pellets of botanical composition, as well as by comparison with results obtained by ICP-MS using solution nebulization after microwave assisted digestion. Plant samples of unknown elemental composition were analyzed by the proposed LA method and good agreement were obtained with results of solution analysis. Limits of detection (LOD) established for LA-ICP-MS were obtained by the ablation of 10 lines on the filter paper disc containing 40 μL of 5% HNO3 (v v(-1)) as calibration blank. Values ranged from 0.05 to 0.81  μg g(-1). Overall, the use of filter paper as support for dried aqueous

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

    NASA Astrophysics Data System (ADS)

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

    2011-01-01

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

  17. Evidence for multi-cycle sedimentation and provenance constraints from detrital zircon U-Pb ages: Triassic strata of the Lusitanian basin (western Iberia)

    NASA Astrophysics Data System (ADS)

    Pereira, M. F.; Gama, C.; Chichorro, M.; Silva, J. B.; Gutiérrez-Alonso, G.; Hofmann, M.; Linnemann, U.; Gärtner, A.

    2016-06-01

    Laser ablation ICP-MS U-Pb analyses were conducted on detrital zircons of Triassic sandstone and conglomerate from the Lusitanian basin in order to: i) document the age spectra of detrital zircon; ii) compare U-Pb detrital zircon ages with previous published data obtained from Upper Carboniferous, Ordovician, Cambrian and Ediacaran sedimentary rocks of the pre-Mesozoic basement of western Iberia; iii) discuss potential sources; and iv) test the hypothesis of sedimentary recycling. U-Pb dating of zircons established a maximum depositional age for this deposit as Permian (ca. 296 Ma), which is about sixty million years older compared to the fossil content recognized in previous studies (Upper Triassic). The distribution of detrital zircon ages obtained points to common source areas: the Ossa-Morena and Central Iberian zones that outcrop in and close to the Porto-Tomar fault zone. The high degree of immaturity and evidence of little transport of the Triassic sediment suggests that granite may constitute primary crystalline sources. The Carboniferous age of ca. 330 Ma for the best estimate of crystallization for a granite pebble in a Triassic conglomerate and the Permian-Carboniferous ages (< ca. 315 Ma) found in detrital zircons provide evidence of the denudation of Variscan and Cimmerian granites during the infilling of continental rift basins in western Iberia. The zircon age spectra found in Triassic strata are also the result of recycling from the Upper Carboniferous Buçaco basin, which probably acted as an intermediate sediment repository. U-Pb data in this study suggest that the detritus from the Triassic sandstone and conglomerate of the Lusitanian basin is derived from local source areas with features typical of Gondwana, with no sediment from external sources from Laurussia or southwestern Iberia.

  18. High-spatial-resolution isotope geochemistry of monazite (U-Pb & Sm-Nd) and zircon (U-Pb & Lu-Hf) in the Old Woman and North Piute Mountains, Mojave Desert, California

    NASA Astrophysics Data System (ADS)

    Phillips, Stacy E.; Hanchar, John M.; Miller, Calvin F.; Fisher, Christopher M.; Lancaster, Penny J.; Darling, James R.

    2014-05-01

    Recent improvements in analytical capabilities allow us to reveal details of magmatic processes at an increasingly finer spatial and temporal scale. In situ analyses of the isotopic and trace element composition of accessory minerals at the sub-grain scale have proven to be effective tools for solving a wide range of geological problems. This study presents new data on accessory minerals including monazite & zircon, examined by in situ LA-ICP-MS and Laser Ablation Split Stream (LASS) techniques, analyzing multiple isotopic systems (U-Pb + Sm-Nd, and U-Pb + Lu-Hf in monazite and zircon, respectively) in order to track geochemical changes over time through a magmatic system. The late Cretaceous granitoids of the Old Woman Mountains in the Mojave Desert, California, provide an excellent opportunity to apply these analytical techniques. The peraluminous granites of the Sweetwater Wash, Painted Rock, and North Piute plutons represent different depths of the magmatic system, and are well understood in terms of field relations and whole-rock geochemistry. A preliminary study on the Sweetwater Wash monazites (Fisher et al., in preparation) has revealed significant inter-grain isotopic heterogeneity in the ɛNd composition of the source region (~1700 Ma); however, the U-Pb ages show an isotopic resetting during emplacement at ~75 Ma. This decoupling of U-Pb and Sm-Nd isotopic systems is suggested by Fisher et al. to be due to recrystallisation and/or dissolution-reprecipitation of monazite. If grain boundary diffusion of Pb overrides the more kinetically limited volume diffusion, then the U-Pb systematics will be reset while Sm and Nd remain immobile in the monazite structure as essential structural components of the lattice. This new data will allow the further investigation of these preliminary results, providing new insights into the observed isotopic disequilibrium, with the LASS technique accurately linking the multiple isotopic systems. This will provide important

  19. Importance of LA-ICP-MS Zircon Geochronology and Geochemistry in Determining the History of Magmatic Systems: Insights from the Graciosa A-type Province, Southern Brazil

    NASA Astrophysics Data System (ADS)

    Braun, S.; Gualda, G. A.; Bream, B. R.; Vlach, S. R.

    2010-12-01

    The Graciosa Province comprises more than 20 A-type granitic and syenitic plutons in southern Brazil. This province was emplaced during a period of tectonic change, with A-type magmatism post-dating syntectonic I- and S-type magmatism to the east. Dating the age of magmatism has proven challenging, with current published results showing a wide range of ages (550-590 Ma), most of which with low analytical resolution (2σ errors >15 Ma). We use Laser Ablation ICP-MS to determine U-Pb ages and trace element compositions of zircon crystals in-situ. We analyzed zircon from ten samples representative of the petrographic diversity observed in the 5 plutons located in the Serra da Graciosa region1, which include monzodiorites, granites, and alkali-feldspar granites and syenites. The graintoids include rocks with aluminous affinity (biotite-bearing), and others with alkaline affinity (sodic amphibole-bearing). Our results show three age populations with concordant ages at ~633±6, 581±3, and 539±4 Ma (all errors 2σ): - The oldest zircon ages come from analyses of zircon cores that display overgrowth and resorption textures. - The majority of zircon grains analyzed yield ages ~581 Ma. Zircons of this age can be found in all but two samples analyzed. Spots yielding these ages come from rim regions free of fractures or inclusions. REE patterns show enrichment in HREE, and pronounced positive Ce anomaly, as typically seen in magmatic zircons. - Strongly altered grains from alkali-feldspar granites with biotite dominate the youngest zircon population. These grains have myriad inclusions of thorite, REE fluorides (fluocerite, CeF3 - confirmed by EBSD), and REE phosphates. A few analyses in other rocks yield similar ages. REE patterns are much less steep for these zircons, and Ce anomalies are much more subdued, as characteristic of hydrothermal zircons. Further, these zircons are enriched in high field-strength elements such as Nb and Hf, as well as in Th and U. Based on

  20. Detrital zircon geochronology by LA-ICP-MS of the Neoarchean Manjeri Formation in the Archean Zimbabwe craton- the disappearance of Eoarchean crust by 2.7 Ga?

    NASA Astrophysics Data System (ADS)

    Sawada, Hikaru; Maruyama, Shigenori; Sakata, Shuhei; Hirata, Takafumi

    2016-01-01

    For the ca. 2.7 Ga (Neoarchean) clastic rocks in the Belingwe greenstone belt (Manjeri Formation), U-Pb age of detrital zircon grains were analyzed by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). The Manjeri Formation, composed of sandstone, quartzite, and limestone with stromatolites, was deposited in a shallow marine setting along the ancient passive continental margin of the Zimbabwe craton. Nearly 100 detrital zircon grains, for each from two sandstone samples in central Zimbabwe, were separated for U-Pb dating. Age spectra of detrital zircon grains of two analyzed sandstones of the Manjeri Formation show more or less the same multiple age clusters: i.e., ca. 2.9 Ga, ca. 3.15 Ga, ca. 3.3 Ga, and ca. 3.5 Ga. These age spectra reflect nature of the provenance of proto-Zimbabwe, which was considerably different from that of the modern Zimbabwe craton. The age clusters of ca. 2.9 Ga, ca. 3.3 Ga, and ca. 3.5 Ga are correlated with those of extant basement rocks of the present Zimbabwe craton, whereas the ca. 3.15 Ga cluster has no corresponding unit within the craton, except for detrital zircons from the 2.65 Ga Shamvaian Group in a neighboring area of the Zimbabwe craton. The extremely old (3.85 Ga; Eoarchean) detrital zircon grains, previously reported from the ca. 2.9 Ga and ca. 3.4 Ga sandstones elsewhere in the craton, were not detected at all in the present two analyzed samples. As no Eoarchean (>3.8 Ga) basement rocks remain in the Zimbabwe craton at present either, the present study confirmed that the Eoarchean crustal rocks once occurred in the proto-Zimbabwe craton but they had been removed secondarily from the provenance of Neoarchean and younger basins prior to 2.7 Ga. Possible geologic processes for such disappearance of older crusts may include the physiological separation by continental rifting, subduction erosion, and/or other crustal recycling processes.

  1. Analysis of some Romanian fruit juices by ICP-MS

    NASA Astrophysics Data System (ADS)

    Dehelean, A.; Magdas, D. A.

    2013-11-01

    The present study was carried out to evaluate the heavy metal content of 21 Romanian single strength fruit (plum, apple, sour cherry) juices. The samples were collected from five Romanian areas namely: Alba, Maramures, Cluj, Salaj and Moldova. The results indicated macro (Na, Mg, Ca, P) and micro (Fe, Zn, Ni, Cr, Cd, Pb, etc) elements in the selected samples. The determination was performed by ICP-MS. Our results for fruit juice were compared with allowable limits for drinking water in the United Kingdom (NS30).

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

    NASA Astrophysics Data System (ADS)

    Peters, Daniel; Pettke, Thomas

    2016-04-01

    An efficient, clean procedure for bulk rock major to trace element analysis by 193 nm Excimer LA-ICP-MS analysis of nanoparticulate pressed powder pellets (PPPs) employing a binder is presented. Sample powders are milled in water suspension in a planetary ball mill, reducing average grain size by about one order of magnitude compared to common dry milling protocols. Microcrystalline cellulose (MCC) is employed as a binder, improving the mechanical strength of the PPP and the ablation behaviour, because MCC absorbs 193 nm laser light well. Use of MCC binder allows for producing cohesive pellets of materials that cannot be pelletized in their pure forms, such as quartz powder. Rigorous blank quantification was performed on synthetic quartz treated like rock samples, demonstrating that procedural blanks are irrelevant except for a few elements at the 10 ng g-1 concentration level. The LA-ICP-MS PPP analytical procedure was optimised and evaluated using six different SRM powders (JP-1, UB-N, BCR-2, GSP-2, OKUM, and MUH-1). Calibration based on external standardization using SRM 610, SRM 612, BCR-2G, and GSD-1G glasses allows for evaluation of possible matrix effects during LA-ICP-MS analysis. The data accuracy of the PPP LA-ICP-MS analytical procedure compares well to that achieved for liquid ICP-MS and LA-ICP-MS glass analysis, except for element concentrations below ˜30 ng g-1, where liquid ICP-MS offers more precise data and in part lower limits of detection. Uncertainties on the external reproducibility of LA-ICP-MS PPP element concentrations are of the order of 0.5 to 2 % (1σ standard deviation) for concentrations exceeding ˜1 μg g-1. For lower element concentrations these uncertainties increase to 5-10% or higher when analyte-depending limits of detection (LOD) are approached, and LODs do not significantly differ from glass analysis. Sample homogeneity is demonstrated by the high analytical precision, except for very few elements where grain size effects can

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

    PubMed

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

    2014-01-01

    In order to quantify and compare the uptake of aluminum oxide nanoparticles of three different sizes into two human cell lines (skin keratinocytes (HaCaT) and lung epithelial cells (A549)), three analytical methods were applied: digestion followed by nebulization inductively coupled plasma mass spectrometry (neb-ICP-MS), direct laser ablation ICP-MS (LA-ICP-MS), and flow cytometry. Light and electron microscopy revealed an accumulation and agglomeration of all particle types within the cell cytoplasm, whereas no particles were detected in the cell nuclei. The internalized Al2O3 particles exerted no toxicity in the two cell lines after 24 h of exposure. The smallest particles with a primary particle size (x BET) of 14 nm (Alu1) showed the lowest sedimentation velocity within the cell culture media, but were calculated to have settled completely after 20 h. Alu2 (x BET = 111 nm) and Alu3 (x BET = 750 nm) were calculated to reach the cell surface after 7 h and 3 min, respectively. The internal concentrations determined with the different methods lay in a comparable range of 2-8 µg Al2O3/cm(2) cell layer, indicating the suitability of all methods to quantify the nanoparticle uptake. Nevertheless, particle size limitations of analytical methods using optical devices were demonstrated for LA-ICP-MS and flow cytometry. Furthermore, the consideration and comparison of particle properties as parameters for particle internalization revealed the particle size and the exposure concentration as determining factors for particle uptake. PMID:25285033

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

    PubMed

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

    2013-03-01

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

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

    SciTech Connect

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

    2012-05-01

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

  6. Sensitive redox speciation of neptunium by CE-ICP-MS.

    PubMed

    Stöbener, Nils; Amayri, Samer; Gehl, Aaron; Kaplan, Ugras; Malecha, Kurtis; Reich, Tobias

    2012-11-01

    Capillary electrophoresis (CE) was used to separate the neptunium oxidation states Np(IV) and Np(V), which are the only oxidation states of Np that are stable under environmental conditions. The CE setup was coupled to an inductively coupled plasma mass spectrometer (Agilent 7500ce) using a Mira Mist CE nebulizer and a Scott-type spray chamber. The combination of the separation capacity of CE with the detection sensitivity of inductively coupled plasma mass spectrometry (ICP-MS) allows identification and quantification of Np(IV) and Np(V) at the trace levels expected in the far field of a nuclear waste repository. Limits of detection of 1 × 10(-9) and 5 × 10(-10) mol L(-1) for Np(IV) and Np(V), respectively, were achieved, with a linear range from 10(-9) to 10(-6) mol L(-1). The method was applied to study the redox speciation of the Np remaining in solution after interaction of 5 × 10(-7) mol L(-1) Np(V) with Opalinus Clay. Under mildly oxidizing conditions, a Np sorption of 31% was found, with all the Np remaining in solution being Np(V). A second sorption experiment performed in the presence of Fe(2+) led to complete sorption of the Np onto the clay. After desorption with HClO(4), a mixture of Np(IV) and Np(V) was found in solution by CE-ICP-MS, indicating that some of the sorbed Np had been reduced to Np(IV) by Fe(2+).

  7. Formation of a magmatic-hydrothermal ore deposit: insights with LA-ICP-MS analysis of fluid inclusions

    PubMed

    Audetat; Gunther; Heinrich

    1998-03-27

    The physical and chemical mechanism of ore precipitation in the Yankee Lode tin deposit (Mole Granite, Australia) was quantified by direct trace-element microanalysis of fluid inclusions. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to measure element concentrations in a series of fluid inclusions representing the fluid before, during, and after the deposition of cassiterite (SnO2). Tin precipitation was driven by mixing of hot magmatic brine with cooler meteoric water. At the same time, a separate magmatic vapor phase selectively transported copper and boron into the liquid mixture.

  8. Formation of a magmatic-hydrothermal ore deposit: insights with LA-ICP-MS analysis of fluid inclusions

    PubMed

    Audetat; Gunther; Heinrich

    1998-03-27

    The physical and chemical mechanism of ore precipitation in the Yankee Lode tin deposit (Mole Granite, Australia) was quantified by direct trace-element microanalysis of fluid inclusions. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to measure element concentrations in a series of fluid inclusions representing the fluid before, during, and after the deposition of cassiterite (SnO2). Tin precipitation was driven by mixing of hot magmatic brine with cooler meteoric water. At the same time, a separate magmatic vapor phase selectively transported copper and boron into the liquid mixture. PMID:9516106

  9. LA-ICP-MS for Pu source identification at Mayak PA, the Urals, Russia.

    PubMed

    Cagno, S; Hellemans, K; Lind, O C; Skipperud, L; Janssens, K; Salbu, B

    2014-02-01

    Information on Pu in environmental samples is traditionally based on the determination of the (240+239)Pu activity via Alpha Spectrometry (AS). A large number of alpha spectrometry sources (planchettes) containing radiochemically separated Pu are therefore stored worldwide and are available for further analyses. These archive samples represent a resource from which valuable information on isotopic composition of alpha emitters including Pu can be obtained. The relative abundances of Pu isotopes can be used to trace specific Pu sources and characterize the relative contributions of different Pu sources in a sample. Thus, in addition to the total (239+240)Pu activity, determination of the (240)Pu/(239)Pu ratio can provide valuable information on the nature of the Pu emitting sources. The Pu isotopic ratios can be determined by mass spectrometry techniques such as Sector Field Inductively Coupled Plasma Mass Spectrometry (SF-ICPMS) or Accelerator Mass Spectrometry (AMS) that require dissolution and complete destruction of the material deposited on the planchettes. In this study Laser Ablation (LA)-quadrupole-ICP-MS has been employed for the analysis of (239)Pu/(240)Pu ratios from alpha-planchettes prepared from samples originating from the Mayak PA nuclear facility, Russia. The results are compared with data from AMS and show that the (240)Pu/(239)Pu ratios obtained by LA-ICP-MS can be utilized to distinguish weapons-grade Pu from civil reprocessing sources. Moreover, isotope ratio mapping can also be performed across the planchettes, allowing e.g. the visualization of possible inhomogeneities in the Pu-isotope distribution on their surface. Thus, this solid sample technique can be applied to extract additional information from existing archives of samples. PMID:24424783

  10. LA-ICP-MS for Pu source identification at Mayak PA, the Urals, Russia.

    PubMed

    Cagno, S; Hellemans, K; Lind, O C; Skipperud, L; Janssens, K; Salbu, B

    2014-02-01

    Information on Pu in environmental samples is traditionally based on the determination of the (240+239)Pu activity via Alpha Spectrometry (AS). A large number of alpha spectrometry sources (planchettes) containing radiochemically separated Pu are therefore stored worldwide and are available for further analyses. These archive samples represent a resource from which valuable information on isotopic composition of alpha emitters including Pu can be obtained. The relative abundances of Pu isotopes can be used to trace specific Pu sources and characterize the relative contributions of different Pu sources in a sample. Thus, in addition to the total (239+240)Pu activity, determination of the (240)Pu/(239)Pu ratio can provide valuable information on the nature of the Pu emitting sources. The Pu isotopic ratios can be determined by mass spectrometry techniques such as Sector Field Inductively Coupled Plasma Mass Spectrometry (SF-ICPMS) or Accelerator Mass Spectrometry (AMS) that require dissolution and complete destruction of the material deposited on the planchettes. In this study Laser Ablation (LA)-quadrupole-ICP-MS has been employed for the analysis of (239)Pu/(240)Pu ratios from alpha-planchettes prepared from samples originating from the Mayak PA nuclear facility, Russia. The results are compared with data from AMS and show that the (240)Pu/(239)Pu ratios obtained by LA-ICP-MS can be utilized to distinguish weapons-grade Pu from civil reprocessing sources. Moreover, isotope ratio mapping can also be performed across the planchettes, allowing e.g. the visualization of possible inhomogeneities in the Pu-isotope distribution on their surface. Thus, this solid sample technique can be applied to extract additional information from existing archives of samples.

  11. Advances in the measurement of sulfur isotopes by multi-collector ICP-MS (MC-ICP- MS)

    NASA Astrophysics Data System (ADS)

    Ridley, W. I.; Wilson, S. A.; Anthony, M. W.

    2006-12-01

    The demonstrated capability to measure 34S/32S by MC-ICP-MS with a precision (2ó) of ~0.2 per mil has many potential applications in geochemistry. However, a number of obstacles limit this potential. First, to achieve the precision indicated above requires sufficient mass resolution to separate isobaric interferences of 16O2 and 17O2 on 32S and 34S, respectively. These requirements for high resolution mean overall instrument sensitivity is reduced. Second, current methods preclude analysis of samples with complex matrices, a common characteristic of sulfur-bearing geologic materials. Here, we describe and discuss a method that provides both efficient removal of matrix constituents, and provides pre-concentration of S, thus overcoming these obstacles. The method involves the separation of sulfur from matrix constituents by high pressure (1000 psi) ion chromatography (HPIC), followed by isotope measurement using MC-ICP-MS. This combination allows for analysis of liquid samples with a wide range of S concentrations. A powerful advantage of this technique is the efficient separation of many sulfur species from matrix cations and anions (for instance in a seawater or acid mine drainage matrix), as well as the separation of sulfur species, e.g., sulfate, sulfite, thiosulfate, thiocynate, from each other for isotope analysis. The automated HPIC system uses a carbonate-bicarbonate eluent with eluent suppression, and has sufficient baseline separation to collect the various sulfur species as pure fractions. The individual fractions are collected over a specific time interval based upon a pre-determined elution profile and peak retention times. The addition of a second ion exchange column into the system allows pre-concentration of sulfur species by 2-3 orders of magnitude for samples that otherwise would have sulfur concentrations too low to provide precise isotopic ratios. The S isotope ratios are measured by MC-ICP-MS using a desolvating sample introduction system, a

  12. No Paleozoic metamorphics in Palawan (the Philippines)? Evidence from single grain U-Pb dating of detrital zircons

    NASA Astrophysics Data System (ADS)

    Walia, Monika; Knittel, Ulrich; Suzuki, Shigeyuki; Chung, Sun-Lin; Pena, Rolando E.; Yang, Tsanyao Frank

    2012-06-01

    The Palawan Continental Terrane (PCT) is a fragment of the margin of SE China that drifted south as a result of the Cenozoic opening of the South China Sea. This fragment is of great interest as it may contain a record of the early history of the continental margin of SE China that is not exposed on the mainland. The age and potential correlations of meta-sediments exposed on Palawan Island, Philippines, with those exposed on the other islands of Philippine Archipelago and Asia are a long standing problem of the geology of this island. Given the presence of non-metamorphic sedimentary sequences of Permian and Triassic age in the northern part of the island, a Paleozoic age was inferred for the metamorphics but recently also a younger age for these rocks was considered possible. U/Pb dating of detrital zircons by the laser-ablation ICP-MS method reveals the presence of 80-98 Ma old zircons in all of the usually distinguished units, hence despite significant differences in degree of metamorphism and tectonic deformation, all meta-sediments appear to be of late Cretaceous or younger age. Thus, in principle, these clastic rocks could be overly derived from the older sequences. However, the relatively higher degree of metamorphism of the younger rocks suggests a tectonic contact with the older sequences.

  13. Double dating of detrital zircon by fission-track and LA-ICPMS U/Pb analysis: new perspectives in decomposing mixed provenance signatures

    NASA Astrophysics Data System (ADS)

    Mikes, Tamás.; Jeffries, Teresa E.; Dunkl, István.; Tolosana-Delgado, Raimon; von Eynatten, Hilmar

    2010-05-01

    A novel approach combining fission track (FT) and in-situ LA-ICPMS U/Pb isotopic analyses in single detrital zircon grains is used to trace the exhumed sources of Tertiary synorogenic sediments in the Dinarides. Grains were dated by the FT method, and their interiors were imaged by SEM-CL to avoid ablation of inherited or other unsuitable domains. U/Pb isotopic compositions were determined by an instrument setup of a 213 nm Nd:YAG laser source coupled to a quadrupole-based ICP-MS, and an analytical protocol providing a cost-effective sample throughput (70-100 grains per day) while maintaining high analytical precision and accuracy. CL-control and a good spatial resolution helped suppressing age bias, as justified by a notably high proportion (>90%) of concordant (±5%) grain ages. Finally, the FT and U/Pb ages were integrated for each grain using a bivariate statistical algorithm that takes the different precisions permitted by the two dating techniques into account. The zircon double dating approach yields valuable insights into the thermal history of source terrains of synorogenic sediments both in the Outer Dinaride foreland basin and in the Dinarides-Tisza collisional zone. We can isolate several clusters of characteristic pairs of crystallization/cooling ages, which pin-point Alpine tectonostratigraphic units with a confidence that could not be achieved by using the two dating techniques separately. The Adriatic basement of the Dinarides affected by the major Jurassic-Early Cretaceous cooling event was not the exclusive source for the siliciclastic fill of these Tertiary basins. The distributary systems involved much detritus from Ordovician and Late Permian magmatic units affected by a Late Cretaceous thermal event; such units are not typical in the Dinarides. A major sediment input from the Austroalpine, Tisza and Pelagonian Units in the Tertiary is the most likely scenario for the evolution of the Dinaride basins.

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

    SciTech Connect

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

    2015-08-17

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  16. Constraining the age of the Mitu Group, South-East Peru: U-Pb ages of detrital and igneous zircons

    NASA Astrophysics Data System (ADS)

    Reitsma, Mariël.; Schaltegger, Urs; Spikings, Richard; Winkler, Wilfried; Carlotto, Victor

    2010-05-01

    Inverted extensional basins with continental deposits of the Mitu Group straddle the Eastern Cordillera of Peru. The present study investigates the Mitu Group of south-east Peru (13-16°S), which consists of continental clastic sedimentary rocks and interbedded basaltic to andesitic lavas. There is a paucity of geochemical and geochronological data from the Mitu Group, and the interpretation of its evolution is complicated by i) rapid changes in fault structure along-strike of the graben system, and ii) inversion during Andean orogenesis. Due to dominating coarse-grained clastics, the Mitu Group is devoid of fossils and its age is poorly bracketed to the Permo-Triassic, based on its stratigraphic relationships with the underlying Copacabana and overlying Pucará groups. The upper strata of the Copacabana Group have been constrained by palynology to the Artinskian, while marine fossils at the base of the Pucará Group indicate a Norian age. The Pucará Group is only present in northern Peru, whereas the Mitu Group has an erosional contact with overlying Cretaceous sandstones in the study area. Preliminary data suggest that the lower Mitu Group is middle Triassic, leaving a significant hiatus between the Copacabana and Mitu groups. Laser ablation ICP-MS U-Pb zircon dating was utilized to characterize pre- and syn-rift detrital zircon assemblages in sandstones, as well as to date the syn-rift volcanic and plutonic activity. Detrital zircon U-Pb age histograms of medium grained sandstones in the pre-rift Ambo and Copacabana groups contain several age populations, which can be immediately linked to major events identified along the western Gondwanan margin, such as the Sunsas/Grenville (1 Ga) and Pampean (0.55 Ga) orogenies, as well as the Famatinian arc (0.45 Ga). The youngest zircon in the population assigns a maximum deposition age to the rock; these zircons are of late Mississippian age for the Ambo and latest Pennsylvanian for the Copacabana groups. The

  17. Integrated single crystal laser ablation U/Pb and (U-Th)/He dating of detrital accessory minerals - Proof-of-concept studies of titanites and zircons from the Fish Canyon tuff

    NASA Astrophysics Data System (ADS)

    Horne, Alexandra M.; van Soest, Matthijs C.; Hodges, Kip V.; Tripathy-Lang, Alka; Hourigan, Jeremy K.

    2016-04-01

    Excimer laser technologies enable a rapid and effective approach to simultaneous U/Pb geochronology and (U-Th)/He thermochronology of a wide range of detrital accessory minerals. Here we describe the 'laser ablation double dating' (LADD) method and demonstrate its viability by applying it to zircon and titanite crystals from the well-characterized Fish Canyon tuff. We found that LADD dates for Fish Canyon zircon (206Pb/238U - 28.63 ± 0.11 Ma; (U-Th)/He - 28.38 ± 0.73 Ma) are statistically indistinguishable from those obtained through established, traditional methods of single-crystal dating. The same is true for Fish Canyon titanite LADD dates: 206Pb/238U - 28.08 ± 0.90 Ma; (U-Th)/He - 27.98 ± 0.86 Ma. As anticipated, given that LADD involves the analysis of smaller amounts of material than traditional methods, it yields dates with higher analytical uncertainty. However, this does not substantially reduce the utility of the results for most applications to detrital datasets. An important characteristic of LADD is that it encourages the chemical characterization of crystals by backscattered electron, cathodoluminescence, and/or Raman mapping prior to dating. In addition, by permitting the rapid and robust dating of crystals regardless of the degree of their abrasion during sedimentary transport, the method theoretically should yield dates that are more broadly representative of those of the entire population of detrital crystals in a natural sample.

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

    PubMed Central

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

    2016-01-01

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

  19. Elemental bioimaging of Cisplatin in Caenorhabditis elegans by LA-ICP-MS

    PubMed Central

    Crone, Barbara; Aschner, Michael; Schwerdtle, Tanja; Karst, Uwe; Bornhorst, Julia

    2015-01-01

    Cis-diamminedichloroplatinum(II) (Cisplatin) is one of the most important and frequently used cytostatic drugs for the treatment of various solid tumors. Herein, a laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) method incorporating a fast and simple sample preparation protocol was developed for the elemental mapping of Cisplatin in the model organism Caenorhabditis elegans (C. elegans). The method allows imaging of the spatially-resolved elemental distribution of platinum in the whole organism with respect to the anatomic structure in L4 stage worms at a lateral resolution of 5 µm. In addition, a dose- and time-dependent Cisplatin uptake was corroborated quantitatively by a total reflection X-ray fluorescence spectroscopy (TXRF) method, and the elemental mapping indicated that Cisplatin is located in the intestine and in the head of the worms. Better understanding of the distribution of Cisplatin in this well-established model organism will be instrumental in deciphering Cisplatin toxicity and pharmacokinetics. Since the cytostatic effect of Cisplatin is based on binding the DNA by forming intra- and interstrand crosslinks, the response of poly(ADP-ribose)metabolism enzyme 1 (pme-1) deletion mutants to Cisplatin was also examined. Loss of pme-1, which is the C. elegans ortholog of human poly(ADP-ribose) polymerase 1 (PARP-1) led to disturbed DNA damage response. With respect to survival and brood size, pme-1 deletion mutants were more sensitive to Cisplatin as compared to wildtype worms, while Cisplatin uptake was indistinguishable. PMID:25996669

  20. Eliminating mass-fractionation effects on U-Pb isochron ages without double spiking

    NASA Astrophysics Data System (ADS)

    Ludwig, Kenneth R.

    2001-09-01

    The utility of uranium-lead isochrons for dating rocks with a restricted range in U/Pb is limited by any uncertainty in the mass fractionation of the analysis. Double spiking (TIMS) or thallium normalization (ICP-MS) remove much of this limitation, as does the method of Getty and DePaolo (1995) for very young rocks. Optimal use of the 3-D "Total Pb/U isochron," however, is extremely simple to apply, requires only single-spiked TIMS analyses, and essentially eliminates fractionation-related age imprecision for rocks of any age.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2008-01-01

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

  3. Zircon U-Pb age of the Pescadero felsite: A late Cretaceous igneous event in the forearc, west-central California Coast Ranges

    USGS Publications Warehouse

    Ernst, W.G.; Martens, U.C.; McLaughlin, R.J.; Clark, J.C.; Moore, Diane E.

    2011-01-01

    Weathered felsite is associated with the late Campanian-Maastrichtian Pigeon Point Formation near Pescadero, California. Poorly exposed, its age and correlation are uncertain. Is it part of the Pigeon Point section west of the San Gregorio-Hosgri fault? Does it rest on Nacimiento block basement? Is it dextrally offset from the Oligocene Cambria Felsite, ~185 km to the southeast? Why is a calc-alkaline hypabyssal igneous rock intrusive into the outboard accretionary prism? To address these questions, we analyzed 43 oscillatory-zoned zircon crystals from three incipiently recrystallized pumpellyite ?? prehnite ?? laumontite-bearing Pescadero felsite samples by sensitive high-resolution ion microprobe-reverse geometry (SHRIMPRG) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) techniques. Thirty-three zircons gave late Mesozoic U-Pb ages, with single-grain values ranging from 81 to 167 Ma; ten have pre-Mesozoic, chiefl y Proterozoic ages. A group of the four youngest Pescadero zircons yielded an apparent maximum igneous age of ca. 86-90 Ma. Refl ecting broad age scatter and presence of partly digested sandstone inclusions, we interpret the rest of the zircons (perhaps all) as xenocrysts. Twenty-three zircons were separated and analyzed from two samples of the similar Cambria Felsite, yielding a unimodal 27 Ma U-Pb age. Clearly, the origin of the Upper Oligocene Cambria Felsite is different from that of the Upper Cretaceous Pescadero felsite; these rocks are not correlated, and do not constrain displacement along the San Gregorio-Hosgri fault. Peak ages differ slightly, but relative probability curves for Mesozoic and pre-Mesozoic Pescadero zircons compare well, for example, with abundant U-Pb age data for detrital zircons from Franciscan metaclastic strata ~100 km to the east in the Diablo Range- San Francisco Bay area, San Joaquin Great Valley Group turbidites, Upper Cretaceous Nacimiento block Franciscan strata, and Upper Cretaceous

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

    PubMed

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

    2016-03-01

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

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

    PubMed

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

    2016-03-01

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

  6. U-Pb zircon age, geochemical and Lu-Hf isotopic constraints of the Southern Gangma Co basalts in the Central Qiangtang, northern Tibet

    NASA Astrophysics Data System (ADS)

    Wang, Ming; Li, Cai; Xie, Chao Ming; Xu, Jian Xin; Li, Xing Kui

    2015-08-01

    A recent study suggests that the central Qiangtang is a key locality to investigate the evolution of the opening and closure of the Paleo-Tethys Ocean. Basalts are commonly associated with supercontinent fragmentation, and they have the potential to indicate the tectonic environment into which they were erupted. In this study, laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) U-Pb zircon dating, whole-rock geochemistry, and zircon Hf isotope analysis were used to study newly discovered basalts in the southern Gangma Co area of central Qiangtang. Dating of magmatic zircons from three basalt samples indicates that the basalts erupted in the Late Devonian to early Carboniferous (early Tournaisian) at 360-350 Ma. The basalts are geochemically similar to within-plate basalts and formed from a depleted mantle source. We suggest that the basalts may have been a product of the breakup of the northern margin of Gondwana in the Late Devonian to early Carboniferous (360-350 Ma), which may be linked to the initial rifting and opening of the Paleo-Tethys Ocean in the Qiangtang area.

  7. LA-ICP-MS Allows Quantitative Microscopy of Europium-Doped Iron Oxide Nanoparticles and is a Possible Alternative to Ambiguous Prussian Blue Iron Staining.

    PubMed

    Scharlach, Constantin; Müller, Larissa; Wagner, Susanne; Kobayashi, Yuske; Kratz, Harald; Ebert, Monika; Jakubowski, Norbert; Schellenberger, Eyk

    2016-05-01

    The development of iron oxide nanoparticles for biomedical applications requires accurate histological evaluation. Prussian blue iron staining is widely used but may be unspecific when tissues contain substantial endogenous iron. Here we tested whether microscopy by laser ablation coupled to inductively coupled plasma mass spectrometry (LA-ICP-MS) is sensitive enough to analyze accumulation of very small iron oxide particles (VSOP) doped with europium in tissue sections. For synthesis of VSOP, a fraction of Fe3+ (5 wt%) was replaced by Eu3+, resulting in particles with 0.66 mol% europium relative to iron (Eu-VSOP) but with otherwise similar properties as VSOP. Eu-VSOP or VSOP was intravenously injected into ApoE-/- mice on Western cholesterol diet and accumulated in atherosclerotic plaques of these animals. Prussian blue staining was positive for ApoE-/- mice with particle injection but also for controls. LA-ICP-MS microscopy resulted in sensitive and specific detection of the europium of Eu-VSOP in liver and atherosclerotic plaques. Furthermore, calibration with Eu-VSOP allowed calculation of iron and particle concentrations in tissue sections. The combination of europium-doped iron oxide particles and LA-ICP-MS microscopy provides a new tool for specific and quantitative analysis of particle distribution at the tissue level and allows correlation with other elements such as endogenous iron.

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

    NASA Astrophysics Data System (ADS)

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

    2007-03-01

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

  9. LA-ICP-MS Allows Quantitative Microscopy of Europium-Doped Iron Oxide Nanoparticles and is a Possible Alternative to Ambiguous Prussian Blue Iron Staining.

    PubMed

    Scharlach, Constantin; Müller, Larissa; Wagner, Susanne; Kobayashi, Yuske; Kratz, Harald; Ebert, Monika; Jakubowski, Norbert; Schellenberger, Eyk

    2016-05-01

    The development of iron oxide nanoparticles for biomedical applications requires accurate histological evaluation. Prussian blue iron staining is widely used but may be unspecific when tissues contain substantial endogenous iron. Here we tested whether microscopy by laser ablation coupled to inductively coupled plasma mass spectrometry (LA-ICP-MS) is sensitive enough to analyze accumulation of very small iron oxide particles (VSOP) doped with europium in tissue sections. For synthesis of VSOP, a fraction of Fe3+ (5 wt%) was replaced by Eu3+, resulting in particles with 0.66 mol% europium relative to iron (Eu-VSOP) but with otherwise similar properties as VSOP. Eu-VSOP or VSOP was intravenously injected into ApoE-/- mice on Western cholesterol diet and accumulated in atherosclerotic plaques of these animals. Prussian blue staining was positive for ApoE-/- mice with particle injection but also for controls. LA-ICP-MS microscopy resulted in sensitive and specific detection of the europium of Eu-VSOP in liver and atherosclerotic plaques. Furthermore, calibration with Eu-VSOP allowed calculation of iron and particle concentrations in tissue sections. The combination of europium-doped iron oxide particles and LA-ICP-MS microscopy provides a new tool for specific and quantitative analysis of particle distribution at the tissue level and allows correlation with other elements such as endogenous iron. PMID:27305821

  10. Efficient analysis of complex natural materials using LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Kent, A. J.; Loewen, M. W.; Koleszar, A. M.; Miller, J.; Ungerer, C. "

    2011-12-01

    Many natural materials exhibit complex variations in chemical or isotopic composition over relatively short length scales, and these compositional variations often record important information about the environment or nature of the processes that lead to formation. Examples include complexly zoned crystals within volcanic rocks that record magmatic and volcanic signals, otoliths and other biominerals that record life history and environmental information, and speleothems that record climatic variables. Laser ablation ICP-MS analyses offer several advantages for quantifying compositional in chemically complex natural materials. These include the speed of analysis, the ability to sample at atmospheric pressures, the wide diversity of possible analytes, and the ability to make measurements in both spot and raster modes. The latter in particular offers advantages for analyses that require efficient acquisition of information over significant length scales, as in raster mode compositional data can be rapidly obtained by translating the laser laterally over a compositional variable material during a single analysis. In this fashion elemental or isotopic composition at a given analysis time corresponds to the lateral spatial dimension. This contrasts with a record obtained by a row of individual spots, which require a large number of discrete analyses, and requires significantly more analysis time. However there are also disadvantages to this style of analysis. Translation of the circular spots typically used for analysis results in significant signal attenuation and production of artifacts that may mirror natural diffusion profiles or other gradual changes. The ability to ablate using non-circular spots significantly reduces this effect, although the degree of attenuation is also increased by slower ablation cell response times. For single volume cells this may result in 50-100% additional attenuation than that produced by the translation of the spot alone, although two

  11. Single Particle ICP-MS: Advances toward routine analysis of nanomaterials.

    PubMed

    Montaño, Manuel D; Olesik, John W; Barber, Angela G; Challis, Katie; Ranville, James F

    2016-07-01

    From its early beginnings in characterizing aerosol particles to its recent applications for investigating natural waters and waste streams, single particle inductively coupled plasma-mass spectrometry (spICP-MS) has proven to be a powerful technique for the detection and characterization of aqueous dispersions of metal-containing nanomaterials. Combining the high-throughput of an ensemble technique with the specificity of a single particle counting technique and the elemental specificity of ICP-MS, spICP-MS is capable of rapidly providing researchers with information pertaining to size, size distribution, particle number concentration, and major elemental composition with minimal sample perturbation. Recently, advances in data acquisition, signal processing, and the implementation of alternative mass analyzers (e.g., time-of-flight) has resulted in a wider breadth of particle analyses and made significant progress toward overcoming many of the challenges in the quantitative analysis of nanoparticles. This review provides an overview of spICP-MS development from a niche technique to application for routine analysis, a discussion of the key issues for quantitative analysis, and examples of its further advancement for analysis of increasingly complex environmental and biological samples. Graphical Abstract Single particle ICP-MS workflow for the analysis of suspended nanoparticles.

  12. Cross-validation and evaluation of the performance of methods for the elemental analysis of forensic glass by μ-XRF, ICP-MS, and LA-ICP-MS.

    PubMed

    Trejos, Tatiana; Koons, Robert; Becker, Stefan; Berman, Ted; Buscaglia, JoAnn; Duecking, Marc; Eckert-Lumsdon, Tiffany; Ernst, Troy; Hanlon, Christopher; Heydon, Alex; Mooney, Kim; Nelson, Randall; Olsson, Kristine; Palenik, Christopher; Pollock, Edward Chip; Rudell, David; Ryland, Scott; Tarifa, Anamary; Valadez, Melissa; Weis, Peter; Almirall, Jose

    2013-06-01

    Elemental analysis of glass was conducted by 16 forensic science laboratories, providing a direct comparison between three analytical methods [micro-x-ray fluorescence spectroscopy (μ-XRF), solution analysis using inductively coupled plasma mass spectrometry (ICP-MS), and laser ablation inductively coupled plasma mass spectrometry]. Interlaboratory studies using glass standard reference materials and other glass samples were designed to (a) evaluate the analytical performance between different laboratories using the same method, (b) evaluate the analytical performance of the different methods, (c) evaluate the capabilities of the methods to correctly associate glass that originated from the same source and to correctly discriminate glass samples that do not share the same source, and (d) standardize the methods of analysis and interpretation of results. Reference materials NIST 612, NIST 1831, FGS 1, and FGS 2 were employed to cross-validate these sensitive techniques and to optimize and standardize the analytical protocols. The resulting figures of merit for the ICP-MS methods include repeatability better than 5% RSD, reproducibility between laboratories better than 10% RSD, bias better than 10%, and limits of detection between 0.03 and 9 μg g(-1) for the majority of the elements monitored. The figures of merit for the μ-XRF methods include repeatability better than 11% RSD, reproducibility between laboratories after normalization of the data better than 16% RSD, and limits of detection between 5.8 and 7,400 μg g(-1). The results from this study also compare the analytical performance of different forensic science laboratories conducting elemental analysis of glass evidence fragments using the three analytical methods.

  13. Current role of ICP-MS in clinical toxicology and forensic toxicology: a metallic profile.

    PubMed

    Goullé, Jean-Pierre; Saussereau, Elodie; Mahieu, Loïc; Guerbet, Michel

    2014-08-01

    As metal/metalloid exposure is inevitable owing to its omnipresence, it may exert toxicity in humans. Recent advances in metal/metalloid analysis have been made moving from flame atomic absorption spectrometry and electrothermal atomic absorption spectrometry to the multi-elemental inductively coupled plasma (ICP) techniques as ICP atomic emission spectrometry and ICP-MS. ICP-MS has now emerged as a major technique in inorganic analytical chemistry owing to its flexibility, high sensitivity and good reproducibility. This in depth review explores the ICP-MS metallic profile in human toxicology. It is now routinely used and of great importance, in clinical toxicology and forensic toxicology to explore biological matrices, specifically whole blood, plasma, urine, hair, nail, biopsy samples and tissues.

  14. Current role of ICP-MS in clinical toxicology and forensic toxicology: a metallic profile.

    PubMed

    Goullé, Jean-Pierre; Saussereau, Elodie; Mahieu, Loïc; Guerbet, Michel

    2014-08-01

    As metal/metalloid exposure is inevitable owing to its omnipresence, it may exert toxicity in humans. Recent advances in metal/metalloid analysis have been made moving from flame atomic absorption spectrometry and electrothermal atomic absorption spectrometry to the multi-elemental inductively coupled plasma (ICP) techniques as ICP atomic emission spectrometry and ICP-MS. ICP-MS has now emerged as a major technique in inorganic analytical chemistry owing to its flexibility, high sensitivity and good reproducibility. This in depth review explores the ICP-MS metallic profile in human toxicology. It is now routinely used and of great importance, in clinical toxicology and forensic toxicology to explore biological matrices, specifically whole blood, plasma, urine, hair, nail, biopsy samples and tissues. PMID:25383735

  15. Element-tagged immunoassay with ICP-MS detection: evaluation and comparison to conventional immunoassays

    PubMed Central

    Razumienko, Eva; Ornatsky, Olga; Kinach, Robert; Milyavsky, Michael; Lechman, Eric; Baranov, Vladimir; Winnik, Mitchell A.; Tanner, Scott D.

    2008-01-01

    We have investigated the possibility of using element-tagged antibodies for protein detection and quantification in microplate format using Inductively Coupled Plasma Mass Spectrometry (ICP-MS), and compared the results to conventional immunoassays, such as Enzyme-Linked Immunosorbent Assay (ELISA) and Western blotting. The technique was further employed to detect low levels and measure DNA-binding activity of transcription factor p53 in leukemia cell lysates through its interaction with immobilized oligonucleotides and recognition by element-tagged antibodies. The advantages of ICP-MS detection for routine performance of immunoassays include increased sensitivity, wide dynamic range, minimal interference from complex matrices, and high throughput. Our approach advances the ICP-MS technology and demonstrates its applicability to proteomic studies through the use of antibodies directly labeled with polymer tags bearing multiple atoms of lanthanides. Development of this novel methodology will enable fast and quantitative identification of multiple analytes in a single well. PMID:18456275

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

    SciTech Connect

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

    2009-10-01

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

  17. Application of isotope dilution ICP-MS techniques to quantitative proteomics.

    PubMed

    Bettmer, Jörg

    2010-08-01

    ICP-MS techniques based on isotope dilution analysis can be regarded as an emerging tool in quantitative protein analysis. Well-known concepts, for example species-specific and unspecific isotope dilution analysis, which promoted accurate and precise quantification in elemental speciation studies, have nowadays been transferred to the analysis of large biomolecules, e.g. proteins. Besides detection of heteroatom-containing proteins, the artificial introduction of metal-containing labels has attracted much attention and, as a consequence, ICP-MS-based isotope dilution techniques can serve as a valuable quantification tool. In particular, because isotope dilution ICP-MS techniques can enable absolute protein quantification, they can be regarded as an attractive technique in current and prospective proteomics. In this review, recent developments and applications will be highlighted and critically assessed.

  18. Imaging of trace element distribution in zircon by LA-ICP-MS: Insights into ultrahigh-pressure anatexis

    NASA Astrophysics Data System (ADS)

    Stepanov, Aleksandr; Danyushevsky, Leonid; Olin, Paul; Meffre, Sebastien; Rubatto, Daniela; Hermann, Joerg; Korsakov, Andrey

    2014-05-01

    Zircon is a key accessory mineral in Ultra High Pressure (UHP) metamorphic rocks as it is stable during the entire metamorphic evolution and it remains as a restite phase after melt extraction. Zircon contains significant amounts of REE, Th and U, elements which, at the bulk-rock scale, are strongly affected by melting at UHP conditions. Due to its refractory nature, zircon can preserve pre-melting concentrations of such elements. Moreover, zircon growth zones can be precisely dated and the Ti-in-zircon thermometer can provide a temperature record. A LA-ICP-MS imaging technique has been developed at the CODES analytical facilities at the University of Tasmania. The technique uses a set of parallel lines with spacing equaling the laser beam size. Pre-ablation of each line is essential for removing surface deposition from previous ablations. Regular measurements of the background and calibration standards are required for controlling memory effects and instrumental drift. Use of square rather than round beam shape is preferred for this application. LA-ICP-MS imaging provides spatial resolution of about 10 microns and detection limits below 1 ppm. High errors on individual measurements are compensated by large overall statistics. Here we report the successful application of this imaging technique to zircons from the Kokchetav metamorphic complex (Kazakhstan). The UHP metamorphic rocks of the Kokchetav complex experienced partial melting and melt loss at extreme conditions of 45-60 kbar and 950-1000°C. Metamorphism of metasediments produced a specific bulk rock trace element signature with depletion in LREE, Th and U. LA-ICP-MS spots analysis and LA-ICP-MS imaging reveal at least four different compositional types of zircon. Type-1 zircon cores have low Th contents and Th/U ratios and steep REE patterns. The low Th content is attributed to formation in equilibrium with monazite, which hosted a large fraction of the bulk Th. Type-2 zircons are seen as mantles with Th

  19. U-Pb geochronology on zircon and columbite-group minerals of the Cap de Creus pegmatites, NE Spain

    NASA Astrophysics Data System (ADS)

    Van Lichtervelde, Marieke; Grand'Homme, Alexis; de Saint-Blanquat, Michel; Olivier, Philippe; Gerdes, Axel; Paquette, Jean-Louis; Melgarejo, Joan Carles; Druguet, Elena; Alfonso, Pura

    2016-08-01

    The Cap de Creus granitic pegmatites in the eastern Catalan Pyrenees were dated using in situ U-Pb geochronology by laser ablation ICP-MS on zircon and columbite-group minerals (CGM), which are present in the different types of pegmatites from type I (K-feldspar pegmatites, least evolved) to type IV (albite pegmatites, most evolved) and therefore allow dating the different pegmatitic pulses. In a type III pegmatite where zircon and CGM are co-genetically associated in the same sample, both minerals were dated using zircon and tantalite reference materials, respectively, to avoid laser-induced matrix-dependent fractionation. In one sample, xenotime genetically associated with zircon was also dated. Two ages were obtained for type I and three ages for type III pegmatites. Three of these 5 ages range from 296.2 ± 2.5 to 301.9 ± 3.8 Ma and are allocated to the primary magmatic stage of crystallization and therefore to the emplacement event. Two younger ages (290.5 ± 2.5 and 292.9 ± 2.9 Ma) obtained on secondary zircon and xenotime, respectively, are interpreted as late post-solidus hydrothermal remobilization. There is no age difference between type I and type III pegmatites. The mean 299 Ma primary magmatic age allows the main late Carboniferous deformation event to be dated and is also synchronous with other peraluminous and calc-alkaline granites in the Pyrenees. However, the youngest ages around 292 Ma imply that tectonics was still active in Early Permian times in the Cap de Creus area.

  20. {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.

  1. Combination of PAGE and LA-ICP-MS as an analytical workflow in metallomics: state of the art, new quantification strategies, advantages and limitations.

    PubMed

    Sussulini, Alessandra; Becker, Johanna Sabine

    2011-12-01

    Metallomics (more specifically, metalloproteomics) is an emerging field that encompasses the role, uptake, transport and storage of trace metals, which are essential to preserve the functions of proteins within a biological system. The current strategies for metal-binding and metalloprotein analysis based on the combination of polyacrylamide gel electrophoresis (PAGE) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) are discussed in this review. The advantages, limitations and the most recently developed and applied quantification approaches for this methodology are also described.

  2. Development of analytical procedures for determination of total chromium by quadrupole ICP-MS and high-resolution ICP-MS, and hexavalent chromium by HPLC-ICP-MS, in different materials used in the automotive industry.

    PubMed

    Séby, F; Gagean, M; Garraud, H; Castetbon, A; Donard, O F X

    2003-10-01

    A European directive was recently adopted limiting the use of hazardous substances such as Pb, Hg, Cd, and Cr(VI) in vehicle manufacturing. From July 2003 a maximum of 2 g Cr(VI) will be authorised per vehicle in corrosion-preventing coatings of key components. As no standardised procedures are available to check if produced vehicles are in agreement with this directive, the objective of this work was to develop analytical procedures for total chromium and Cr(VI) determination in these materials. The first step of this study was to optimise digestion procedures for total chromium determination in plastic and metallic materials by inductively coupled plasma mass spectrometry (ICP-MS). High resolution (HR) ICP-MS was used to examine the influence of polyatomic interferences on the detection of the (52)Cr(+) and (53)Cr(+) isotopes. If there was strong interference with m/ z 52 for plastic materials, it was possible to use quadrupole ICP-MS for m/ z 53 if digestions were performed with HNO(3)+H(2)O(2). This mixture was also necessary for digestion of chromium from metallic materials. Extraction procedures in alkaline medium (NH(4)(+)/NH(3) buffer solution at pH 8.9) assisted by sonication were developed for determining Cr(VI) in four different corrosion-preventing coatings by HPLC-ICP-MS. After optimisation and validation with the only solid reference material certified for its Cr(VI) content (BCR 545; welding dusts), the efficiency of this extraction procedure for screw coatings was compared with that described in the EN ISO 3613 standard generally used in routine laboratories. For coatings comprising zinc and aluminium passivated in depth with chromium oxides the extraction procedure developed herein enabled determination of higher Cr(VI) concentrations. This was also observed for the screw covered with a chromium passivant layer on zinc-nickel. For coating comprising a chromium passivant layer on alkaline zinc the standardized extraction procedure was more efficient

  3. Elemental Analysis of Carbonaceous Chondrites by Sector Field ICP-MS

    NASA Astrophysics Data System (ADS)

    Braukmüller, N.; Escoube, R.; Münker, C.; Heuser, A.; Wombacher, F.

    2016-08-01

    CM chondrites are analyzed via SF-ICP MS for a comparison of the chemical compositions of antarctic and non-antarctic CM chondrites. Aliquots of Murchison CM2 chondrite powder have been heated in a tube furnace to study the loss of volatile elements.

  4. Petrogenesis of Augite-bearing Ureilites: A LA-ICP-MS Approach

    NASA Astrophysics Data System (ADS)

    Huang, S.; Humayun, M.; Downes, H.; Singletary, S.; van Orman, J. A.; Jacobsen, S. B.

    2009-03-01

    Major, minor and trace elements have been determined on silicate minerals from ureilites LAR 04315, North Haig and FRO 93008 using LA-ICP-MS. The element compositions in ureilite minerals are consistent with ureilites being melting/smelting restites from a spinel peridotite.

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

    SciTech Connect

    Dion, Michael P.; Liezers, Martin; Farmer, Orville T.; Miller, Brian W.; Morley, Shannon M.; Barinaga, Charles J.; Eiden, Gregory C.

    2015-01-01

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

  6. Accurate and precise determination of isotopic ratios by MC-ICP-MS: a review.

    PubMed

    Yang, Lu

    2009-01-01

    For many decades the accurate and precise determination of isotope ratios has remained a very strong interest to many researchers due to its important applications in earth, environmental, biological, archeological, and medical sciences. Traditionally, thermal ionization mass spectrometry (TIMS) has been the technique of choice for achieving the highest accuracy and precision. However, recent developments in multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) have brought a new dimension to this field. In addition to its simple and robust sample introduction, high sample throughput, and high mass resolution, the flat-topped peaks generated by this technique provide for accurate and precise determination of isotope ratios with precision reaching 0.001%, comparable to that achieved with TIMS. These features, in combination with the ability of the ICP source to ionize nearly all elements in the periodic table, have resulted in an increased use of MC-ICP-MS for such measurements in various sample matrices. To determine accurate and precise isotope ratios with MC-ICP-MS, utmost care must be exercised during sample preparation, optimization of the instrument, and mass bias corrections. Unfortunately, there are inconsistencies and errors evident in many MC-ICP-MS publications, including errors in mass bias correction models. This review examines "state-of-the-art" methodologies presented in the literature for achievement of precise and accurate determinations of isotope ratios by MC-ICP-MS. Some general rules for such accurate and precise measurements are suggested, and calculations of combined uncertainty of the data using a few common mass bias correction models are outlined.

  7. Ionic gold in calcrete revealed by LA-ICP-MS, SXRF and XANES

    SciTech Connect

    Lintern, Melvyn J.; Hough, Robert M.; Ryan, Chris G.; Watling, John; Verrall, Michael

    2009-04-02

    Highly anomalous Au concentrations in calcrete were discovered in 1987 at the Bounty Gold Deposit, Western Australia. A strong correlation was noted between the Ca, Mg, Sr and Au in soil profiles which have not only attracted the interest of mineral explorers but also chemists, soil scientists, metallurgists and climatologists. Gold has been considered an inert element and so its strong association with the alkaline earth group of relatively mobile elements is both remarkable and intriguing. Despite widespread interest, there have been few published papers on the Au-calcrete phenomenon. Here, we present work conducted on calcareous soil samples from above the Bounty mineralization in Western Australia, prior to mining. Using SXRF (synchrotron X-ray fluorescence) and XANES (micro-X-ray absorption near-edge structure), we have shown for the first time the distribution of Au in calcrete and that it occurs in both particulate and ionic form. Much of the ionic Au associated with Br is found in a root tubule. The observations are consistent with an evapotranspiration model for the formation of Au in the calcrete; Au has been mobilized then precipitated as vadose water has been removed from the soil by trees and shrubs. While the association between Au and Ca is very strong in bulk sample analyses down the soil profile, other detailed analyses on sub-samples using wet chemical, LA-ICP-MS (laser ablation inductively coupled mass spectrometry) and SXRF techniques show that it is not apparent at the sub-millimeter scale. This suggests that the Au and Ca are behaving similarly but independently and they do not (at the {micro}m scale) co-precipitate with carbonate minerals. These results corroborate other studies that suggest biotic influences can affect the mobilization and distribution of Au in surficial materials. Water-extractable Au in calcrete has been reported previously and the ionic Au described in this study likely represents that soluble component. The presence of

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

    NASA Astrophysics Data System (ADS)

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

    2006-08-01

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

  9. Potassium Stable Isotopic Compositions Measured by High-Resolution MC-ICP-MS

    NASA Technical Reports Server (NTRS)

    Morgan, Leah E.; Lloyd, Nicholas S.; Ellam, Robert M.; Simon, Justin I.

    2012-01-01

    Potassium isotopic (K-41/K-39) compositions are notoriously difficult to measure. TIMS measurements are hindered by variable fractionation patterns throughout individual runs and too few isotopes to apply an internal spike method for instrumental mass fractionation corrections. Internal fractionation corrections via the K-40/K-39 ratio can provide precise values but assume identical K-40/K-39 ratios (e.g. 0.05% (1sigma) in [1]); this is appropriate in some cases (e.g. identifying excess K-41) but not others (e.g., determining mass fractionation effects and metrologically traceable isotopic abundances). SIMS analyses have yielded measurements with 0.25% precisions (1sigma) [2]. ICP-MS analyses are significantly affected by interferences from molecular species such as Ar-38H(+) and Ar-40H(+) and instrument mass bias. Single collector ICP-MS instruments in "cold plasma" mode have yielded uncertainties as low as 2% (1sigma, e.g. [3]). Although these precisions may be acceptable for some concentration determinations, they do not resolve isotopic variation in terrestrial materials. Here we present data from a series of measurements made on the Thermo Scientific NEPTUNE Plus multi-collector ICP-MS that demonstrate the ability to make K-41/K-39 ratio measurements with 0.07% precisions (1sigma). These data, collected on NIST K standards, indicate the potential for MC-ICP-MS measurements to look for K isotopic variations at the sub-permil level. The NEPTUNE Plus can sufficiently resolve 39K and 41K from the interfering 38ArH+ and 40ArH+ peaks in wet cold plasma and high-resolution mode. Measurements were made on small but flat, interference-free, plateaus (ca. 50 ppm by mass width for K-41). Although ICP-MS does not yield accurate K-41/K-39 values due to significant instrumental mass fractionation (ca. 6%), this bias can be sufficiently stable over the time required for several measurements so that relative K-41/K-39 values can be precisely determined via sample

  10. First U-Pb isotopic data on zircon from andesite of the Saf'yanovka Cu-bearing massive sulfide deposit (Middle Urals)

    NASA Astrophysics Data System (ADS)

    Ronkin, Yu. L.; Pritchin, M. E.; Soroka, E. I.; Gerdes, A.; Puchkov, V. N.; Busharina, S. V.

    2016-07-01

    New results of U-Pb LA ICP-MS dating of zircon from andesite samples cropping out on the western wall of the Saf'yanovka quarry (57°22'58.88″ N, 61°31'50.85″ E) in the synonymous Cu-Zn-bearing massive sulfide deposit of the Urals type are considered. The position of data points of the U-Pb systematics in the 207Pb/235U-206Pb/238U plot determines a cluster practically corresponding to the concordant U-Pb age: 422.8 ± 2.0 Ma. This date indicates for the first time the presence of Pridolian volcanogenic rocks in the East Urals megazone of the Middle Urals.

  11. Quantitative determination of bromine and iodine in food samples using ICP-MS.

    PubMed

    Nguyen, Thi Kim Dzung; Ludwig, Rainer

    2014-01-01

    Trace concentrations of bromine and iodine in food samples and certified reference materials (CRMs) were determined by an inductively coupled plasma-mass spectrometry (ICP-MS) technique after low-power microwave digestion and extraction into an aqueous quaternary ammonium hydroxide solution. The recovery after sample preparation was quantitative. The internal standard for the measurement of the analyte on ICP-MS was optimized in this study. The detection limits were 0.19 and 0.68 ng g(-1) for I and Br, respectively, when a 10 ng g(-1) Te solution as an internal standard was used, applying the signal of (125)Te. The high recovery and reproducibility are sufficient for the quantitative analysis of these elements, and the analytical procedure is recommended for the analysis of Br and I in various kinds of bio-samples.

  12. Development of ICP-MS based nanometrology techniques for characterization of silver nanoparticles in environmental systems

    NASA Astrophysics Data System (ADS)

    Mitrano, Denise Marie

    The ubiquitous use of goods containing nanoparticles (NPs) will lead inevitably to environmental release and interaction with biota. Methods to detect, quantify, and characterize NPs in environmental matrices are highlighted as one of the areas of highest priority research in understanding potential environmental and health risks. Specifically, techniques are needed to determine the size and concentration of NPs in complex matrices. Particular analytical challenges include distinguishing NPs from other constituents of the matrix (i.e. natural particles, humic substances, and debris), method detection limits are often higher than exposure concentrations, and differentiating dissolved metal and NPs. This work focuses on the development and optimization of two methods that address a number of challenges for nanometrology: single particle (sp)ICP-MS and asymmetrical flow field flow fractionation (AF4)-ICP-MS. Advancements in the spICP-MS method included systematic studies on distinction between ionic and NP fractions, resolution of polydisperse NP samples, and defining the techniques' dynamic range (in terms of both particle size and concentration). Upon application of the technique, silver (Ag) NPs were discovered in raw wastewater treatment plant influent and effluent. Furthermore, methodical Ag NP stability studies determined the influence of particle capping agents and water chemistry parameters in a variety of synthetic, natural and processed waters. Method development for AF4-ICP-MS revolved around optimizing run conditions (i.e. operational flows, carrier fluid, membrane choice) to study detection limits, sample recovery, and resolution of polydisperse samples. Practical studies included sizing Ag NP in a sediment-dwelling, freshwater oligochaete (Lumbriculus variegatus) and the kinetics of accumulation of protein bound Ag+. In direct comparison, spICP-MS was found to be more versatile with less sample preparation and lower total analyte detection limit (ng/L vs

  13. Methods for the Detection and Characterization of Silica Colloids by Microsecond spICP-MS.

    PubMed

    Montaño, Manuel D; Majestic, Brian J; Jämting, Åsa K; Westerhoff, Paul; Ranville, James F

    2016-05-01

    The rapid development of nanotechnology has led to concerns over their environmental risk. Current analytical techniques are underdeveloped and lack the sensitivity and specificity to characterize these materials in complex environmental and biological matrices. To this end, single particle ICP-MS (spICP-MS) has been developed in the past decade, with the capability to detect and characterize nanomaterials at environmentally relevant concentrations in complex environmental and biological matrices. However, some nanomaterials are composed of elements inherently difficult to quantify by quadrupole ICP-MS due to abundant molecular interferences, such as dinitrogen ions interfering with the detection of silicon. Three approaches aimed at reducing the contribution of these background molecular interferences in the analysis of (28)Si are explored in an attempt to detect and characterize silica colloids. Helium collision cell gases and reactive ammonia gas are investigated for their conventional use in reducing the signal generated from the dinitrogen interference and background silicon ions leaching from glass components of the instrumentation. A new approach brought on by the advent of microsecond dwell times in single particle ICP-MS allows for the detection and characterization of silica colloids without the need for these cell gases, as at shorter dwell times the proportion of signal attributed to a nanoparticle event is greater relative to the constant dinitrogen signal. It is demonstrated that the accurate detection and characterization of these materials will be reliant on achieving a balance between reducing the contribution of the background interference, while still registering the maximum amount of signal generated by the particle event. PMID:27055808

  14. HPLC/ICP-MS in combination with "reverse" online isotope dilution in drug metabolism studies.

    PubMed

    Meermann, Björn; Hulstaert, Anne; Laenen, Aline; Van Looveren, Cis; Vliegen, Maarten; Cuyckens, Filip; Vanhaecke, Frank

    2012-03-01

    During the development of a new drug compound, its metabolism needs to be unraveled. For quantification of the metabolites formed, the drug under investigation is traditionally synthesized with a radiolabel ((14)C or (3)H) and the metabolites present in different matrixes (blood, urine, feces) upon drug administration are determined by means of high-performance liquid chromatography (HPLC) coupled to radiodetection. This approach allows for quantification of the metabolites formed and enables a straightforward distinction between exogenous (i.e., drug-related) and endogenous species (as only the radiolabeled species are detected). However, in some cases, the use of a radiolabeled compound in human in vivo studies is not advisible, e.g., for drug compounds or their metabolites showing a long plasma or tissue half-life. In cases where the candidate drug molecule contains an element detectable by means of inductively coupled plasma mass spectrometry (ICP-MS), HPLC/ICP-MS is a promising alternative approach. However, the method lacks specificity when a distinction between drug-related species and endogenous compounds containing the same target element needs to be accomplished. As a result, we have developed an HPLC/ICP-MS-based method combined with "reverse" online isotope dilution ("reverse" online ID) for metabolite quantification. The methodology was evaluated by the analysis of feces samples from rats dosed with a (81)Br-labeled drug compound. The method allows for both (i) valid quantification of the drug metabolites and (ii) distinction among endogenous, exogenous, and "mixed" species, based on their isotopic "fingerprint". A good repeatability (relative standard deviation of 4.2%) and limit of detection (0.35 mg of drug compound L(-1) of feces extract), of the same order of magnitude as those observed for "normal" online ID HPLC/ICP-MS and HPLC/radiodetection, were achieved.

  15. Methods for the Detection and Characterization of Silica Colloids by Microsecond spICP-MS.

    PubMed

    Montaño, Manuel D; Majestic, Brian J; Jämting, Åsa K; Westerhoff, Paul; Ranville, James F

    2016-05-01

    The rapid development of nanotechnology has led to concerns over their environmental risk. Current analytical techniques are underdeveloped and lack the sensitivity and specificity to characterize these materials in complex environmental and biological matrices. To this end, single particle ICP-MS (spICP-MS) has been developed in the past decade, with the capability to detect and characterize nanomaterials at environmentally relevant concentrations in complex environmental and biological matrices. However, some nanomaterials are composed of elements inherently difficult to quantify by quadrupole ICP-MS due to abundant molecular interferences, such as dinitrogen ions interfering with the detection of silicon. Three approaches aimed at reducing the contribution of these background molecular interferences in the analysis of (28)Si are explored in an attempt to detect and characterize silica colloids. Helium collision cell gases and reactive ammonia gas are investigated for their conventional use in reducing the signal generated from the dinitrogen interference and background silicon ions leaching from glass components of the instrumentation. A new approach brought on by the advent of microsecond dwell times in single particle ICP-MS allows for the detection and characterization of silica colloids without the need for these cell gases, as at shorter dwell times the proportion of signal attributed to a nanoparticle event is greater relative to the constant dinitrogen signal. It is demonstrated that the accurate detection and characterization of these materials will be reliant on achieving a balance between reducing the contribution of the background interference, while still registering the maximum amount of signal generated by the particle event.

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

    PubMed

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

    2005-06-01

    A sector field high-resolution (HR)-ICP-MS and an octapole reaction system (ORS)-ICP-MS have been compared for the simultaneous determination of traces of metals (Ti, V, Cr, Co, Ni, and Mo) released from dental implants and articular prostheses in human biological fluids. Optimum sample treatments were evaluated to minimize matrix effects in urine and whole blood. Urine samples were diluted tenfold with ultrapure water, whereas whole blood samples were digested with high-purity nitric acid and hydrogen peroxide and finally diluted tenfold with ultrapure water. In both matrices, internal standardization (Ga and Y) was employed to avoid potential matrix interferences and ICP-MS signal drift. Spectral interferences arising from the plasma gases or the major components of urine and whole blood were identified by (HR)-ICP-MS at 3,000 resolving power. The capabilities of (HR)-ICP-MS and (ORS)-ICP-MS for the removal of such spectral interferences were evaluated and compared. Results indicate that polyatomic interferences, which hamper the determination of such metallic elements in these biological samples, could be overcome by using a resolving power of 3,000. Using (ORS)-ICP-MS, all those elements could be quantified except Ti and V (due to the polyatomic ions 31P16O and 35Cl16O, respectively). The accuracy of the proposed methodologies by (HR)- and (ORS)-ICP-MS was checked against two reference materials. Good agreement between the given values and the concentrations obtained for all the analytes under scrutiny was found except for Ti and V when analyzed by (ORS)-ICP-MS. PMID:15877222

  17. Fast Scanning Single Collector ICP-MS for Low Level Isotope Ratio Measurements

    NASA Astrophysics Data System (ADS)

    Newman, K.; Georg, B.

    2010-12-01

    Multiple collector (MC)-ICP-MS is recognized as a workhorse in the field of isotope ratio measurements. With its unrivalled precision, high sample throughput and multi-element coverage, MC-ICPMS has opened up new areas of study in earth, environmental and biological sciences. However, SC-ICP-MS is fit for purpose for many applications where sample amount is limited and fractionations are relatively large. To compensate for the inherent ion beam instability associated with the ICP ion source, fast scanning magnetic sector instruments are used. Here, we describe and discuss the use of the Nu Attom SC-ICP-MS for low level isotope ratio measurements. The Nu Attom is a double focusing magnetic sector mass spectrometer with unique fast scanning capabilities. Deflectors located at the entrance and exit of the flight tube are used to alter the effective magnet radius by changing the ion trajectory. This enables a fast electrostatic scan over a mass range of approximately 40%. In contrast to other fast scanning magnetic sector instruments, there is no change in the ion energy which may introduce additional mass bias effects. The Nu Attom also has fully adjustable source and collector slits. This facilitates measurements in medium mass resolution (R=1500-2500), whilst maintaining a flat topped peak necessary for precise isotope ratio measurements. The potential applications of the Nu Attom in isotope ratio measurements will be explored.

  18. Alternative approach to post column online isotope dilution ICP-MS.

    PubMed

    Swart, Claudia; Rienitz, Olaf; Schiel, Detlef

    2011-02-15

    An alternative post column online double isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS) method was developed. The resulting equation allows a straightforward calculation of the mass concentration of the analyte in the sample from the measured isotope ratio chromatogram. The use of a balance to determine and monitor the mass flow of the spike and a solution of the species under investigation as the reference are the two core components of this new method. Changes in the viscosity of the system eluent-analyte-spike will not affect the results due to the direct determination of the mass flow rate. The use of the species under investigation as the reference makes the method independent of the injected volume. To simplify matters, the integration of the isotope ratio chromatogram was done with Excel using Simpson's rule instead of sophisticated programs for transformation and integration. The advantages of the new approach were demonstrated with the help of the determination of selenomethionine in the selenized yeast reference material SELM-1 with liquid chromatography coupled to ICP-MS (HPLC ID-ICP-MS) applying the new online double IDMS method.

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

    USGS Publications Warehouse

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

    2008-01-01

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

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

    SciTech Connect

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

    2013-08-08

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

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

    SciTech Connect

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

    2013-08-08

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

  2. Fingerprinting of ground water by ICP-MS; Progress report, July 1, 1991--December 31, 1991

    SciTech Connect

    Stetzenbach, K.

    1991-12-31

    The purpose of this project is to investigate the use of minor constituents of ground water and vadose zone water such as the rare earths and some lighter elements, to delineate ground water flow paths and recharge zones in the Yucca Mountain area. The major piece of equipment required to perform this task is an inductively coupled plasma-mass spectrometer (ICP-MS). This instrument has been purchased and should be delivered in February 1992. During this reporting period, three ICP-MS systems were evaluated the Perkin-Elmer Elan 5000 was chosen. As part of the evaluation process, samples of J-13 water and tuff were prepared and analyzed by each of the competing companies. This gave us the opportunity to make initial observations as to the number of compounds and their concentrations present in the J-13 samples. Table 1 lists the results of the analysis of J-13 water. Once the ICP-MS is operational, we will be collecting and analyzing waters from existing wells, springs, and seeps to determine which of these minor chemical constituents will be most helpful in establishing chemical signatures for the ground waters beneath Yucca Mountain.

  3. Assessment of CE-ICP/MS hyphenation for the study of uranyl/protein interactions.

    PubMed

    Huynh, Thi-Ngoc Suong; Bourgeois, Damien; Basset, Christian; Vidaud, Claude; Hagège, Agnès

    2015-06-01

    Identification of uranyl transport proteins is key to develop efficient detoxification approaches. Therefore, analytical approaches have to be developed to cope with the complexity of biological media and allow the analysis of metal speciation. CE-ICP/MS was used to combine the less-intrusive character and high separation efficiency of CE with the sensitive detection of ICP/MS. The method was based on the incubation of samples with uranyl prior to the separation. Electrophoretic buffers were compared to select a 10 mM Tris to 15 mM NaCl buffer, which enabled analyses at pH 7.4 and limited dissociation. This method was applied to the analysis of a serum. Two main fractions were observed. By comparison with synthetic mixtures of proteins, the first one was attributed to fetuin and in a lesser extent to HSA, and the second one to uranyl unbound to proteins. The analysis showed that fetuin was likely to be the main target of uranyl. CE-ICP/MS was also used to investigate the behavior of the fetuin-uranyl complex, in the presence of carbonate, an abundant complexing agent of uranyl in blood. This method enabled association constants determination, suggesting the occurrence of both FETUA(UO2(2+)) and FETUA(UO2(2+))(CO3(2-)) complexes, depending on the carbonate concentration. PMID:25630637

  4. Tandem mass spectrometry in metallomics and the involving role of ICP-MS detection: a review.

    PubMed

    Vogiatzis, C G; Zachariadis, G A

    2014-03-28

    Metallomics is a relatively new branch of omics with a growing interest. The study of metallomes is becoming more focused in certain metabolites and the screening of various categories of analytes using a robust analytical methodology is more than appealing. In this context, when dealing with the challenge of identifying a certain species or specify a particular molecular structure, tandem mass spectrometry (MS/MS) is a reliable tool. Moreover, MS/MS instrumentation is recommended in hyphenated chromatographic techniques with MS detection such as LC-MS, where primary molecular species suffer minor fragmentation (soft-ionization techniques). ICP-MS is widely used in metallomics with its main advantages being the provided high sensitivity and selectivity. Usually, analyzes utilize ICP-MS as the main detection. Its role in proteomics is significant as an alternating choice for protein and peptide quantifications. In this review, we discuss modern trends and applications of MS/MS in the important and growing field of metallomics. These reports concern the identification, characterization and determination of various metal species such as metalloproteins, metallo-DNA adducts, metal-labeled molecules and other metal binding biomolecules. Such assays also present new and interesting hyphenated instrumentation and novel sophisticated apparatus. In addition, we designate the role of ICP-MS in the mentioned contributions and in the same scope we highlight some general analytical strategies.

  5. Arsenic speciation in chinese seaweeds using HPLC-ICP-MS and HPLC-ES-MS.

    PubMed

    Van Hulle, Marijn; Zhang, Chao; Zhang, Xinrong; Cornelis, Rita

    2002-05-01

    Three common Chinese edible seaweeds, one brown (Laminaria japonica) and two red (Porphyra crispata and Eucheuma denticulatum), were examined for their total arsenic content. The As species were extracted with yields of 76.4, 69.8 and 25.0%, respectively. Anion-exchange and cation-exchange high-performance liquid chromatography (HPLC) in combination with inductively coupled plasma mass spectrometry (ICP-MS) were used for the separation of the different arsenic species in two of the three seaweed extracts (Laminaria and Porphyra). The main arsenic species in the algal extracts are arseno sugars, although it has been shown that the Laminaria seaweed contains significant amounts of dimethylarsinic acid (DMA). HPLC was coupled with electrospray mass spectrometry (ES-MS) for structural confirmation of the arsenic species. The mass spectrometer settings for the arseno sugars were optimised using standards. The conclusions drawn on the basis of HPLC-ICP-MS were confirmed by the HPLC-ES-MS data. The HPLC-ES-MS method is capable of determining both arseno sugars and DMA in the seaweeds. The unknown compounds seen in the HPLC-ICP-MS chromatogram of Laminaria could not be ascribed to trimethylarsenic oxide or tetramethylarsonium ion. PMID:12081041

  6. Application of a new HPLC-ICP-MS method for simultaneous determination of Al(3+) and aluminium fluoride complexes.

    PubMed

    Zioła-Frankowska, Anetta; Kuta, Jan; Frankowski, Marcin

    2015-10-01

    The paper presents the new HPLC-ICP-MS method used for conducting speciation analysis of aluminum as free Al(3+) and aluminum fluoride complexes during one analysis. In the study, 5% HNO3 was used as a derivative reagent in order to minimize the possibility of clogging the torch in ICP-MS. Using the new HPLC-ICP-MS method, speciation analysis of aluminum and aluminum fluoride complexes was conducted on the basis of model solutions and real samples (soil-water extracts and groundwater samples). The analysis in the presented analytical system lasts only 4 min. PMID:27441221

  7. Zircon U-Pb geochronology and Sr-Nd isotopes of volcanic rocks from the Dahalajunshan Formation: implications for Late Devonian-Middle Carboniferous tectonic evolution of the Chinese Western Tianshan

    NASA Astrophysics Data System (ADS)

    Yu, Xinqi; Wang, Zongxiu; Zhou, Xiang; Xiao, Weifeng; Yang, Xinpeng

    2016-07-01

    The widespread Late Devonian-Middle Carboniferous volcanic rocks in the Chinese Western Tianshan provide important constraints on the subduction history of the South Tianshan oceanic lithosphere. Here, we investigate the basalt, basaltic andesite, andesite, trachyandesite, and rhyolite from the Dahalajunshan Formation from Western Tianshan. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) U-Pb zircon geochronology constrains their age of formation to between 376 and 333 Ma (i.e., Late Devonian-Middle Carboniferous) with distinct variation in space (from west to east) and time (from early to late). Based on geochemical, zircon geochronological, and Sr-Nd isotopic data, we demonstrate that the Dahalajunshan volcanic was generated in a continental arc setting associated with the subduction of the south Tianshan Ocean during Late Devonian to Middle Carboniferous. The volcanic rocks belonging to Dahalajunshan Formation in the northwestern part of the Yili Block suggest that the northward subduction of the south Tianshan Ocean was initiated in the Early Devonian; those in the southern and eastern part of the Yili Block were probably produced by a northward subduction of South Tianshan Ocean during Late Devonian to Middle Carboniferous.

  8. Timing of the Late Cretaceous ignimbrite flare-up at the eastern margin of the Eurasian Plate: New zircon U-Pb ages from the Aioi-Arima-Koto region of SW Japan

    NASA Astrophysics Data System (ADS)

    Sato, Daisuke; Matsuura, Hirohisa; Yamamoto, Takahiro

    2016-01-01

    The Kinki district in the Inner Zone of southwest Japan is characterized by Late Cretaceous volcanic rocks of the Aioi and Arima groups and the Koto Rhyolites (from west to east). These rocks are dominated by pyroclastic flow deposits related to caldera-forming events. Here, we present new laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) zircon U-Pb ages for the Aioi Group (four isolated caldera-filling deposits); the lower, middle, and upper parts of the Arima Group and one intrusive rock (the Kashihara Quartz Gabbro); and the lower and upper parts of the Koto Rhyolites, including the oldest volcanic unit within these rhyolites. These analyses yielded ages of ca. 86-82 Ma for the Aioi Group, ca. 83-81 Ma for the Arima Group, 78.6 Ma for the Kashihara Quartz Gabbro, and ca. 74-73 Ma for the Koto Rhyolites. The Aioi Group represents a cluster of calderas and the ages obtained for individual units in this group differ from the ages of adjacent units. The Arima Group and the Koto Rhyolites both consist of pyroclastic flow deposits associated with caldera-forming events, and the ages of these rocks are all the same within error. This suggests that the Aioi Group represents a series of individual caldera-forming eruptions that are distinct from the Arima Group and the Koto Rhyolites, which formed during a single stage of caldera formation. The U-Pb ages presented here indicate that the Late Cretaceous caldera-forming eruptions in the study area occurred at intervals of > 1 Myr and represent individual events that lasted for < 1 Myr. The oldest volcanic unit within the Kinki district is similar in age to the oldest volcanic unit within the Chubu district, suggesting that caldera-forming eruptions in southwest Japan commenced at ca. 90 Ma.

  9. Zircon U-Pb geochronology and Sr-Nd-Hf isotopic compositions of the Yuanzhuding granitoid porphyry within the Shi-Hang Zone, South China: Petrogenesis and implications for Cu-Mo mineralization

    NASA Astrophysics Data System (ADS)

    Zhong, Lifeng; Li, Jie; Peng, Touping; Xia, Bin; Liu, Liwen

    2013-09-01

    The Shi-Hang Zone is an important NE-SW-trending Mesozoic magmatic belt in South China, which is dominated by granites with relatively high εNd(t) values and young TDM model ages. Here, we present laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) zircon U-Pb ages, major and trace element compositions, and Sr-Nd-Hf isotope data for the Yuanzhuding porphyritic granitoids within the southwestern Shi-Hang Zone, and use these data to determine the origin of this granitoid and its relationship with Cu-Mo mineralization. Zircon U-Pb dating indicates that these granitoids were emplaced at 157.8 ± 1.1 Ma. They have initial 87Sr/86Sr ratios of 0.70941-0.71398, εNd(t) values of - 3.15 to - 2.02, and in situ zircon εHf(t) values of + 1.71 to + 6.17. Geochemically, most of them are high-K calc-alkaline and show an adakitic affinity. They are more likely emplaced in a continental arc setting related to westward subduction of the paleo-Pacific plate. Their parental magma originated chiefly from the overlying sediments of the downgoing slab, and subsequently interacted with the lithospheric mantle wedge at the temperatures of ~ 790 °C. High oxygen fugacity during magmatic evolution played a crucial role in the development of Cu-Mo mineralization within the Yuanzhuding. The discovery of the Yuanzhuding deposit implies that the Chenzhou-Huaiji fault belt is most likely prospective for mineral exploration for porphyry Cu-Mo deposits.

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

    NASA Technical Reports Server (NTRS)

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

    2014-01-01

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

  11. Zircon U-Pb ages and geochemical characteristics of granitoids in Nagqu area, Tibet

    NASA Astrophysics Data System (ADS)

    Sun, Sai-Jun; Sun, Wei-Dong; Zhang, Li-Peng; Zhang, Rong-Qing; Li, Cong-Ying; Zhang, Hong; Hu, Yong-Bin; Zhang, Zhao-Rong

    2015-08-01

    This paper reports zircon LA-ICP-MS U-Pb ages and Hf-O isotopic ratios, and whole-rock major and trace element data of Early Cretaceous felsic intrusive rocks from Nagqu area, the northern Lhasa subterrane, southern Tibet. LA-ICP-MS zircon U-Pb dating of biotite granites and biotite monzogranites in the area yields magmatic crystallization ages of ca. 112 Ma, which suggests that they were emplaced in the late Early Cretaceous. Both rocks show high-K calc-alkaline to shoshonitic composition and slightly-moderately peraluminous signature. They are enriched in the alkalis, Rb, Th, K, U and light rare earth elements, depleted in Nb, Ta, Ti and P, and characterized by high Al2O3 contents (12-16 wt.%), high Rb/Sr ratios (1.3-33) and low Mg# values (15-39). Their magmatic zircons have negative εHf(t) values (from - 25.9 to 0.5) and high positive δ18O values (from 7.9‰ to 11.5‰). All the above characteristics indicate that Nagqu biotite monzogranites and biotite granites were likely derived from hybrid melts of sediments from the continent crust with minor mantle-derived input, then experienced varied degrees of fractional crystallization. The Nagqu intrusion is a component of the late Early Cretaceous magmatic flare-up event that occurred during ~ 120-100 Ma in the northern and partly central Lhasa subterranes. This magmatic flare-up is marked with a great compositional diversity (basalt, rhyolite, adakitic rocks, dioritic enclave, biotite monzogranite and granite) that might be caused by the slab breakoff of the southward subducting Bangong-Nujiang oceanic lithosphere, or more likely by slab window opening, which may have significantly contributed to juvenile crustal growth of the northern Lhasa subterrane.

  12. Refining LA-ICP-MS techniques for the exploration of ultra-thin layers in Alpine and Polar ice

    NASA Astrophysics Data System (ADS)

    Spaulding, Nicole; Bohleber, Pascal; Mayewski, Paul; Wagenbach, Dietmar; Kurbatov, Andrei; Sneed, Sharon; Handley, Mike; Erhardt, Tobias

    2015-04-01

    Laser ablation inductively coupled plasma mass spectrometry, (LA)-ICP-MS, offers minimally destructive ice core impurity analysis at unsurpassed sub-mm depth resolution. As such it is uniquely suited for exploring the closely spaced layers of ice cores collected in low accumulation sites or in regions of compressed and thinned ice. Here we present an updated characterization of the LA system developed at the University of Maine Climate Change Institute's Keck Laser Ice Facility, as determined through 1) experimentation with sticks of frozen distilled water and 2) exploitation of the exceptionally thin layers within a new ice core drilled at the Alpine glacier saddle Colle Gnifetti (4450m asl, Monte Rosa, Swiss-Italian Alps) and the variety of high-density chemical data collected from it. Colle Gnifetti (CG) is characterized by low net accumulation rates and strong vertical shear, which causes its annual layers to rapidly thin below the cm-resolution of conventional ice core analysis techniques. To best utilize its unique archive, LA measurements of Ca and Na were directly compared to those from continuous flow analysis. Through this comparison, we demonstrate that LA captures low frequency trends similar to traditional melting techniques while also emphasizing the benefits of its increased resolution. The resolution was itself verified through experimental determination of peak decay times, where peaks were created by spiking frozen distilled water at known interval with high concentration riverine water standards. Using ion chromatography and liquid-based ICP-MS measurements of discrete meltwater samples from CG we were also able to explore high-resolution profiles of S as measured by LA. The ability to resolve S at sub-mm resolution (a capability not yet demonstrated for LA analysis of ice cores) may allow more accurate determination of the character and timing of volcanic eruptions. We illustrate this finding using an exemplary S-anomaly, potentially of volcanic

  13. High precision 11B/10B analysis with a simplified MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Tanimizu, M.; Nagaishi, K.

    2012-04-01

    Boron isotope ratio is a powerful tracer in the fields of geochemistry, biochemistry, and environmental chemistry. One important application of 11B/10B isotope ratio in geochemistry is as an indicator for paleo pH of seawater recorded in marine carbonates in deep-sea sediments. Boron isotope ratios are determined by TIMS or MC-ICP-MS with precisions of better than 0.1 % RSD, but a large inter-lab discrepancy of 0.6 % is still observed for actual carbonate samples (Foster, 2008). Here, we tried to determine B isotope ratio by MC-ICP-MS with a simple and common analytical techniques using a quartz sample introduction system with a PFA nebulizer, and compared to recently developed precise B isotope ratio analysis techniques by TIMS in positive ion detection mode determined as Cs2BO2+ ions with sample amount of <100 ng (Ishikawa and Nagaishi, 2011) and by MC-ICP-MS (Foster, 2008, Louvat et al., 2011). 11B/10B isotope ratios of a 50 ppb B solution dissolved in a HNO3, mannitol, HF-mixed solution were determined against an isotopic reference NIST-SRM 951 with a standard sample bracketing technique in the wet plasma condition. Resultant analytical reproducibility (twice standard deviation) was +/-0.02 % with a consumption of 50 ng B, and the washout time was comparable to that of NH3 gas addition to the introduction system (Foster, 2008). 11B/10B isotope ratios of actual carbonate sample and seawater were determined after simple chemical purification with a common cation exchange resin instead of a boron selective resin. Their relative differences from the standard were consistent with those determined by the positive TIMS within analytical uncertainty. Current potential of MC-ICP-MS for precise B isotopic analysis will be discussed. Foster, G., 2008. Seawater pH, pCO2 and [CO32-] variations in the Caribbean Sea over the last 130kyr: A boron isotope and B/Ca study of planktic foraminifera, Earth Planet. Sci. Lett., 271, 254-266. Ishikawa, T. and Nagaishi, K., 2011. High

  14. Nanoparticle size detection limits by single particle ICP-MS for 40 elements.

    PubMed

    Lee, Sungyun; Bi, Xiangyu; Reed, Robert B; Ranville, James F; Herckes, Pierre; Westerhoff, Paul

    2014-09-01

    The quantification and characterization of natural, engineered, and incidental nano- to micro-size particles are beneficial to assessing a nanomaterial's performance in manufacturing, their fate and transport in the environment, and their potential risk to human health. Single particle inductively coupled plasma mass spectrometry (spICP-MS) can sensitively quantify the amount and size distribution of metallic nanoparticles suspended in aqueous matrices. To accurately obtain the nanoparticle size distribution, it is critical to have knowledge of the size detection limit (denoted as Dmin) using spICP-MS for a wide range of elements (other than a few available assessed ones) that have been or will be synthesized into engineered nanoparticles. Herein is described a method to estimate the size detection limit using spICP-MS and then apply it to nanoparticles composed of 40 different elements. The calculated Dmin values correspond well for a few of the elements with their detectable sizes that are available in the literature. Assuming each nanoparticle sample is composed of one element, Dmin values vary substantially among the 40 elements: Ta, U, Ir, Rh, Th, Ce, and Hf showed the lowest Dmin values, ≤10 nm; Bi, W, In, Pb, Pt, Ag, Au, Tl, Pd, Y, Ru, Cd, and Sb had Dmin in the range of 11-20 nm; Dmin values of Co, Sr, Sn, Zr, Ba, Te, Mo, Ni, V, Cu, Cr, Mg, Zn, Fe, Al, Li, and Ti were located at 21-80 nm; and Se, Ca, and Si showed high Dmin values, greater than 200 nm. A range of parameters that influence the Dmin, such as instrument sensitivity, nanoparticle density, and background noise, is demonstrated. It is observed that, when the background noise is low, the instrument sensitivity and nanoparticle density dominate the Dmin significantly. Approaches for reducing the Dmin, e.g., collision cell technology (CCT) and analyte isotope selection, are also discussed. To validate the Dmin estimation approach, size distributions for three engineered nanoparticle samples were

  15. A new LA-ICP-MS method for Ti-in-Quartz: Implications and application to HP rutile-quartz veins from the Czech Erzgebirge

    NASA Astrophysics Data System (ADS)

    Cruz-Uribe, A. M.; Mertz-Kraus, R.; Zack, T.; Feineman, M. D.; Woods, G.

    2014-12-01

    Experimental determination of the pressure and temperature controls on Ti solubility in quartz provide a calibration of the Ti-in-quartz (TitaniQ) geothermometer applicable to geologic conditions up to ~20 kbar (Thomas et al. (2010) Contrib Mineral Petrol 160, 743-759). One of the greatest limitations to analyzing Ti in metamorphic quartz by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is the lack of a suitable matrix-matched reference material. Typically LA-ICP-MS analyses of Ti in minerals use 49Ti as a normalizing mass because of an isobaric interference from 48Ca, which is present in most well characterized reference glasses, on 48Ti. The benefit of using a matrix-matched reference material to analyze Ti in quartz is the opportunity to use 48Ti (73.8 % abundance) as a normalizing mass, which results in an order of magnitude increase in signal strength compared to the less abundant isotope 49Ti (5.5 % abundance), thereby increasing the analytical precision. Here we characterize Ti-bearing SiO2 glasses from Heraeus Quarzglas and natural quartz grains from the Bishop Tuff by cathodoluminescence (CL) imaging, electron probe microanalysis (EPMA), and LA-ICP-MS, in order to determine their viability as reference materials for Ti in quartz. Titanium contents in low-CL rims in the Bishop Tuff quartz grains were determined to be homogenous by EPMA (41 ± 2 µg/g Ti, 2σ), and are a potential natural reference material. We present a new method for determining 48Ti concentrations in quartz by LA-ICP-MS at the 1 µg/g level, relevant to quartz in HP-LT terranes. We suggest that natural quartz such as the homogeneous low-CL rims of the Bishop Tuff quartz are more suitable than NIST reference glasses as an in-house reference material for low Ti concentrations because matrix effects are limited and Ca isobaric interferences are avoided, thus allowing for the use of 48Ti as a normalizing mass. Titanium concentration from 33 analyses of low

  16. Detection of phosphorylated subunits by combined LA-ICP-MS and MALDI-FTICR-MS analysis in yeast mitochondrial membrane complexes separated by blue native/SDS-PAGE

    NASA Astrophysics Data System (ADS)

    Krause-Buchholz, Udo; Becker, J. Susanne; Zoriy, Miroslav; Pickhardt, Carola; Przybylski, Michael; Rödel, Gerhard; Becker, J. Sabine

    2006-01-01

    We report on the identification of phosphorylated subunits of yeast mitochondrial ATPase using a novel screening technique in combination with BN/SDS-PAGE. Protein complexes present in yeast mitochondrial membranes were separated in their native state in the first dimension and their subunit composition was resolved by SDS-PAGE in the second dimension. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to rapidly screen for the presence of phosphorus in the subunits. The detection limits of elements investigated in selected protein spots are in the low [mu]g g-1 concentration range. Sulfur was used as the internal standard element for quantification. Phosphorus was detected in two of the proteins, that were identified by matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry (MALDI-FTICR-MS) as subunits Atp1p and Atp2p of the ATPase. These results were confirmed by Western blot analysis using antibodies directed against phosphorylated amino acids. The combination of LA-ICP-MS and MALDI-FTICR-MS with BN/SDS-PAGE provides a fast and sensitive tool for structure analysis of phosphorus and metal-containing subunits of membrane protein complexes.

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

    SciTech Connect

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

    2012-03-01

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

  18. Determination of trace elements on polysilicates by ID-ICP-MS with ultrasonic nebulization/membrane desolvation

    SciTech Connect

    Bonchin-Cleland, S.; Olivares, J.A.; Miller, G.G.; Gallegos, L.; Dawson, H.J.

    1996-06-01

    This work investigates the performance of an ID-ICP-MS (isotope dilution-inductively coupled plasma mass spectrometry) system with USN/MD (ultrasonic nebulization/membrane desolvation) sample introduction for the determination of trace metal impurities in polysilicon.

  19. In Situ Analysis of Orthopyroxene in Diogenites Using Laser Ablation ICP-MS

    NASA Technical Reports Server (NTRS)

    Elk, Mattias; Quinn, J. E.; Mittlefehldt, D. W.

    2012-01-01

    Howardites, eucrites and diogenites (HED) form a suit of igneous achondrite meteorites that are thought to have formed on a single asteroidal body. While there have been many different models proposed for the formation of the HED parent asteroid they can be generalized into two end member models. One is the magma ocean model (e.g. [1]) in which the entire HED parent body was continuously fractionated from a planet wide magma ocean with diogenites representing the lower crust and eucrites being upper crustal rocks. The second model hypothesizes that diogenites and eucrites were formed as a series of intrusions and/or extrusions of partial melts of a primitive proto-Vesta [2]. We use in situ trace element analysis together with major and minor element analysis to try and distinguish between these different hypotheses for the evolution of the HED parent body.

  20. Exploring LA-ICP-MS as a quantitative imaging technique to study nanoparticle uptake in Daphnia magna and zebrafish (Danio rerio) embryos.

    PubMed

    Böhme, Steffi; Stärk, Hans-Joachim; Kühnel, Dana; Reemtsma, Thorsten

    2015-07-01

    The extent and the mechanisms by which engineered nanoparticles (ENPs) are incorporated into biological tissues are a matter of intensive research. Therefore, laser ablation coupled to inductively coupled plasma mass spectrometry (LA-ICP-MS) is presented for the detection and visualization of engineered nanoparticles (Al2O3, Ag, and Au) in ecotoxicological test organisms (Danio rerio and Daphnia magna). While ENPs are not taken up by the zebrafish embryo but attach to its chorion, incorporation into the gut of D. magna is clearly visible by a 50-μm spot ablation of 40-μm-thick organism sections. During laser ablation of the soft organic matrix, the hard ENPs are mobilized without a significant change in their size, leading to decreasing sensitivity with increasing size of ENPs. To compensate for these effects, a matrix-matched calibration with ENPs of the same size embedded in agarose gels is proposed. Based on such a calibration, the mass of ENPs within one organism section was calculated and used to estimate the total mass of ENPs per organism. Compared to the amount determined after acid digestion of the test organisms, recoveries of 20-100% (zebrafish embryo (ZFE)) and of 4-230% (D. magna) were obtained with LODs in the low ppm range. It is likely that these differences are primarily due to an inhomogeneous particle distribution in the organisms and to shifts in the particle size distribution from the initial ENPs to those present in the organism. It appears that quantitative imaging of ENPs with LA-ICP-MS requires knowledge of the particle sizes in the biological tissue under study.

  1. Post hoc interlaboratory comparison of single particle ICP-MS size measurements of NIST gold nanoparticle reference materials.

    PubMed

    Montoro Bustos, Antonio R; Petersen, Elijah J; Possolo, Antonio; Winchester, Michael R

    2015-09-01

    Single particle inductively coupled plasma-mass spectrometry (spICP-MS) is an emerging technique that enables simultaneous measurement of nanoparticle size and number quantification of metal-containing nanoparticles at realistic environmental exposure concentrations. Such measurements are needed to understand the potential environmental and human health risks of nanoparticles. Before spICP-MS can be considered a mature methodology, additional work is needed to standardize this technique including an assessment of the reliability and variability of size distribution measurements and the transferability of the technique among laboratories. This paper presents the first post hoc interlaboratory comparison study of the spICP-MS technique. Measurement results provided by six expert laboratories for two National Institute of Standards and Technology (NIST) gold nanoparticle reference materials (RM 8012 and RM 8013) were employed. The general agreement in particle size between spICP-MS measurements and measurements by six reference techniques demonstrates the reliability of spICP-MS and validates its sizing capability. However, the precision of the spICP-MS measurement was better for the larger 60 nm gold nanoparticles and evaluation of spICP-MS precision indicates substantial variability among laboratories, with lower variability between operators within laboratories. Global particle number concentration and Au mass concentration recovery were quantitative for RM 8013 but significantly lower and with a greater variability for RM 8012. Statistical analysis did not suggest an optimal dwell time, because this parameter did not significantly affect either the measured mean particle size or the ability to count nanoparticles. Finally, the spICP-MS data were often best fit with several single non-Gaussian distributions or mixtures of Gaussian distributions, rather than the more frequently used normal or log-normal distributions.

  2. [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.

  3. [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. PMID:23747664

  4. A Multi-Method Approach to Improving Monazite Geochronology: TIMS, LA-ICP-MS, SIMS and EPMA

    NASA Astrophysics Data System (ADS)

    Peterman, E. M.; Hacker, B. R.; Grove, M.; Gehrels, G. E.; Mattinson, J. M.

    2006-12-01

    A challenging aspect of monazite U-Th-Pb analysis by LA-ICPMS or other `in situ' methods relates to how to appropriately standardize measured inter-element ratios in this compositionally variable phase. A major impediment is the lack of widely available and compositionally appropriate standards. At UCSB, we have characterized three monazite samples: `Madagascar' (B. Schultz), `Jefferson County' (M. Bersch), and `Smithsonian' (Smithsonian Institution). Grains were analyzed by multicollector ID-TIMS in the static multi- collection mode to establish precise U-Pb ages. Inclusion free grains from each sample were fully digested in HCl and loaded onto filaments using silica gel. We obtained 206Pb/238U ages of 363.98 ± 0.74 Ma for the Jefferson County monazite, 511.25 ± 4.91 Ma for the Madagascar sample and 274.58 ± 0.58 Ma for the Smithsonian sample. Jefferson County and Madagascar are reversely discordant, which is partly attributed to `excess' 206Pb from the decay of 230Th. U, Th, and Pb isotopic measurements were undertaken by multicollector LA-ICPMS at UA. The He carrier gases have sufficiently low Hg abundance that any Hg in the 204 mass position was subtracted by measuring on-peak backgrounds prior to sample analysis. Using the well-characterized monazite sample `44069' (J. Aleinikoff) as a primary standard, we obtained 206Pb/238U of 365.5 ± 2.6 Ma for Jefferson County, 1416 ± 29 Ma for Madagascar, and 357.1 ± 4.9 Ma for Smithsonian. Measured Th-Pb ages were 360.0 ± 4.6 Ma, 1345 ± 39 Ma, and 262.1 ± 4.1 Ma respectively. Ion microprobe Th-Pb ages obtained at UCLA from the same materials were 411 ± 12 Ma, 571 ± 18 Ma, and 327 ± 16 Ma using 44069 as a standard. The discrepancies among U-Pb and Th-Pb ages measured with the three methods clearly indicates that we have much to learn regarding standard-based in situ analysis of monazite. To quantify polyatomic species interference on targeted masses, we analyzed a synthetic CePO4 on the LA-ICPMS at UA. Data

  5. Improved Accuracy and Precision in LA-ICP-MS U-Th/Pb Dating of Zircon through the Reduction of Crystallinity Related Bias

    NASA Astrophysics Data System (ADS)

    Matthews, W.; McDonald, A.; Hamilton, B.; Guest, B.

    2015-12-01

    The accuracy of zircon U-Th/Pb ages generated by LA-ICP-MS is limited by systematic bias resulting from differences in crystallinity of the primary reference and that of the unknowns being analyzed. In general, the use of a highly crystalline primary reference will tend to bias analyses of materials of lesser crystallinity toward older ages. When dating igneous rocks, bias can be minimized by matching the crystallinity of the primary reference to that of the unknowns. However, the crystallinity of the unknowns is often not well constrained prior to ablation, as it is a function of U and Th concentration, crystallization age, and thermal history. Likewise, selecting an appropriate primary reference is impossible when dating detrital rocks where zircons with differing ages, protoliths, and thermal histories are analyzed in the same session. We investigate the causes of systematic bias using Raman spectroscopy and measurements of the ablated pit geometry. The crystallinity of five zircon reference materials with ages between 28.2 Ma and 2674 Ma was estimated using Raman spectroscopy. Zircon references varied from being highly crystalline to highly metamict, with individual reference materials plotting as distinct clusters in peak wavelength versus Full-Width Half-Maximum (FWHM) space. A strong positive correlation (R2=0.69) was found between the FWHM for the band at ~1000 cm-1 in the Raman spectrum of the zircon and its ablation rate, suggesting the degree of crystallinity is a primary control on ablation rate in zircons. A moderate positive correlation (R2=0.37) was found between ablation rate and the difference between the age determined by LA-ICP-MS and the accepted ID-TIMS age (ΔAge). We use the measured, intra-sessional relationship between ablation rate and ΔAge of secondary references to reduce systematic bias. Rapid, high-precision measurement of ablated pit geometries using an optical profilometer and custom MatLab algorithm facilitates the implementation

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

    PubMed

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

    2016-01-01

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

  7. Determination of Boron Isotope Ratios in Coral Skeletons Using Multiple Collector ICP- MS

    NASA Astrophysics Data System (ADS)

    Lin, P.; You, C.; Huang, K.; Wang, B.; Yu, T.

    2008-12-01

    Boron isotopic compositions in biogenic carbonates are useful proxy for oceanic pH in the past. This information is essential for a better understanding of possible mechanisms that control environmental and climate change. A high-precision analytical technique was developed for isotopic determination of boron in coral skeletons using high-resolution multiple collector ICP-MS (MC-ICP-MS, Neptune, Thermo-Fisher). The mass discrimination was corrected by the sample-standard bracketing method. The main advantage of this technique is that both of sample throughput and analytical precision are significantly higher than P-TIMS and N-TIMS. The accuracy of this technique is further examined by replicated analyses of the international coral standard, Jcp-1, and in-house coral standard using both MC-ICP-MS and P-TIMS techniques. The long-lived massive coral skeletons (Porites lobata) from Lanyu Island offshore the southeastern Taiwan show annual δ 11B variation of around 2‰, 23.81 to 25.86‰ (n=39) during 1994 to 1996 A.D., which is similar to recent results from Flinders Reef in the Coral Sea. In combination with Sr/Ca-based thermometry, the intra-annual pH record shows clear seasonal cycles with high pH at cold period. B/Ca and U/Ca ratios also show a good correlation with Sr/Ca derived SSTs. Further in-depth δ 11B applications would help us to understand relationships between the global climate change and response in the surface ocean.

  8. A new method for 44Ca/40Ca determination using cool plasma MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Fietzke, J.; Eisenhauer, A.; Liebetrau, V.; Bock, B.; Gussone, N.; Nägler, T. F.; Dietzel, M.; Spero, H.; Bijma, J.; Dullo, C.

    2003-04-01

    Here we present a new technique for the direct measurement of 44Ca/40Ca isotope ratios on a MC-ICP-MS (Axiom) using the "cool plasma" technique. By reducing the plasma energy from about 1250 Watts to 400 Watts the isobaric effect resulting from 40Ar^+ can be significantly reduced enabling the simultaneous and precise measurement of 44Ca and 40Ca beam intensities in different Faraday cups. In contrast to the TIMS technique requiring a Ca double spike the isotope measurements on a MC-ICP-MS can be performed by bracketing standards. This reduces the effort for chemical preparations without loss of precision. Isobaric effects of MgO^+ and NaOH^+ interfering with 40Ca and MgOH_2 with 44Ca can be neglected by measuring Ca isotopes near the low mass edge of the peaks. No influences of Sr2+ were found monitoring on 43.5amu. Repeated measurements of two Johnson Matthey CaCO_3 standards (lot No. 4064 and lot No. 9912) revealed values of about -11.29 ppm and 0.57 ppm. These values are in accordance with previous values published by Russel et al. (1978) and Heuser et al. (2002). Repeated measurement of the NIST 915a CaCO_3 standard showed that the variance of a single δ44Ca measurement is about 0.28 ppm (2SD) being comparable with TIMS. MC-ICP-MS based δ44Ca values measured on inorganic precipitates are indistinguishable from earlier measurements of Gussone et al. (in press) based on TIMS δ44Ca measurements confirming that there is a positive δ44Ca-temperature gradient. Our study demonstrates the possibility to measure the whole dispersion of Ca isotopes with a MC-ICP-MS showing that 40Ca can be used for normalization of 44Ca. References Russel W. A. et al. (1978) Ca isotope fractionation on the Earth and other solar system materials. Geochim. Cosmochim. Acta 42, 1075--1090. Heuser A. et al. (2002) Measurement of Calcium Isotopes (δ44Ca) Using a Multicollector TIMS Technique. Int. J. Mass Spec. 220, 387--399. Gussone N. et al. (in press) Model for Kinetic Effects on

  9. Ultra-fast HPLC-ICP-MS analysis of oxaliplatin in patient urine.

    PubMed

    Koellensperger, Gunda; Hann, Stephan

    2010-05-01

    A novel method for rapid HPLC-ICP-MS analysis of oxaliplatin in human urine was developed implementing a stationary HPLC phase with a particle size of 1.8 microm. The method allowed a cycle time of <1 min at a HPLC flow rate of 0.9 mL min(-1). Procedural limits of detection of 0.05 microg L(-1) oxaliplatin (150 fg on column) were obtained. Analysis of oxaliplatin in patient urine showed that accurate quantification of the intact drug demanded for storage at -80 degrees C and rapid measurement after thawing.

  10. Determination of δ88/86Sr Using Matrix Correction by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Zhu, B.; Yang, T.; Bian, X. P.; Zhu, Z. Y.

    2014-12-01

    Stable Sr isotopic compositions (δ88/86Sr) in marine carbonates potentially provide key information on paleoseawater temperature (Rüggeberg et al. 2008). Traditional methods for δ88/86Sr determination by 87Sr-84Sr double-spike TIMS or MC-ICP-MS require chemical purification of Sr before spectrometric measurements because of matrix effects. Recent studies suggested that the matrix-matching method, in which matrix-matched standard solutions were used to bracket untreated water samples, gave precise and accurate results for sulfur isotopic ratios by MC-ICP-MS (Lin et al., 2014). The obvious advantage of this method is that there is no need for chemical purification, thus eliminating the possibility of isotope fractionation during the ion chromatography and expediting sample throughput. In this study, we applied the matrix-matching method to δ88/86Sr determination by MC-ICP-MS. NIST 987 Sr solution and a purified seawater sample (collected from the South China Sea) were selected for this study. Given that major matrices in carbonate come form Ca2+, NIST 987 and SW solutions containing 40 ppm Ca2+ were prepared by adding high-purity Ca solution. All solutions used contained 200 ppb Sr and the 88Sr/86Sr ratios were measured using a Neptune MC-ICP-MS. The purified SW was first determined using SSB method, in which pure NIST 987 was used as standard to bracket SW and yielded δ88/86Sr value of 0.366 ± 0.008‰ (2SE, n = 10). The δ88/86Sr values of Ca-bearing SW were then measured by using pure NIST 987 solution as the working standard to investigate matrix effects. The determined δ88/86Sr value (0.039 ± 0.021‰; 2SE, n = 10) deviated obviously from the reference value. Finally, the matrix-matched NIST 987 was applied as the working standard to bracket the Ca-bearing SW, and the measured δ88/86Sr value is 0.351 ± 0.009‰ (2SE, n = 10), consistent with the reference value within uncertainties. The consistent δ88/86Sr values and comparable external precision

  11. [Determination of 27 elements in Maca nationality's medicine by microwave digestion ICP-MS].

    PubMed

    Yu, Gui-fang; Zhong, Hai-jie; Hu, Jun-hua; Wang, Jing; Huang, Wen-zhe; Wang, Zhen-zhong; Xiao, Wei

    2015-12-01

    An analysis method has been established to test 27 elements (Li, Be, B, Mg, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Sr, Mo, Cd, Sn, Sb, Ba, La, Hg, Pb, Bi) in Maca nationality's medicine with microwave digestion-ICP-MS. Sample solutions were analyzed by ICP-MS after microwave digestion, and the contents of elements were calculated according to their calibration curves, and internal standard method was adopted to reduce matrix effect and other interference effects. The experimental results showed that the linear relations of all the elements were very good; the correlation coefficient (r) was 0.9994-1.0000 (Hg was 0.9982) ; the limits of detection were 0.003-2.662 microg x L(-1); the relative standard deviations for all elements of reproducibility were lower than 5% (except the individual elements); the recovery rate were 78.5%-123.7% with RSD lower than 5% ( except the individual elements). The analytical results of standard material showed acceptable agreement with the certified values. This method was applicable to determinate the contents of multi-elements in Maca which had a high sensitivity, good specificity and good repeatability, and provide basis for the quality control of Maca. PMID:27141662

  12. ICP-MS determination of lead isotope ratios in legal and counterfeit cigarette tobacco samples.

    PubMed

    Judd, Christopher D; Swami, Kamal

    2010-12-01

    A method for the determination of Pb isotope ratios (IR) in cigarette tobacco by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) has been developed and applied to tobacco samples from genuine and counterfeit cigarettes obtained in the USA. The IR ²⁰⁷Pb/²⁰⁶Pb, (208)Pb/²⁰⁶Pb, ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb were measured using a Q-ICP-MS instrument. Two certified reference materials, grown in the USA and Bulgaria, were also analysed for comparison with the tobacco samples, as were tobacco samples from cigarettes obtained in Pakistan and China. The precision of the results was sufficient to distinguish between the counterfeit and genuine USA cigarettes. All of the genuine cigarettes and both reference materials, grown in different regions, were statistically distinct based on the measured ratios. The counterfeit cigarettes were indistinguishable from the reference material grown in Bulgaria. The technique shows promise as a method for identifying counterfeit cigarettes, possibly determining the source region.

  13. Specific determination of bromate in bread by ion chromatography with ICP-MS.

    PubMed

    Akiyama, Takumi; Yamanaka, Michiko; Date, Yukiko; Kubota, Hiroki; Nagaoka, Megumi Hamano; Kawasaki, Yoko; Yamazaki, Takeshi; Yomota, Chikako; Maitani, Tamio

    2002-12-01

    A sensitive method for detecting bromate in bread by ion chromatography with inductively-coupled plasma mass spectrometry (IC/ICP-MS) was developed. Bromate was extracted from bread with water. The clean-up procedure included a 0.2 micron filter, a C18 cartridge for defatting, a silver cartridge to remove halogen anions, a centrifugal ultrafiltration unit to remove proteins, and a cation-exchange cartridge to remove silver ions. A 500 microL sample solution was applied to IC/ICP-MS. The detection limit and the quantitation limit of bromate in the solution were 0.3 ng/mL and 1.0 ng/mL, expressed as HBrO3, respectively, which corresponded to 2 ng/g and 5 ng/g, respectively, in bread. Recovery of bromate was about 90%, and the CV was about 2%. Based on the detection limit in solution and recovery from bread, the detection limit of bromate in bread was estimated to be 2 ng/g.

  14. A lead isotope distribution study in swine tissue using ICP-MS

    USGS Publications Warehouse

    May, T.W.; Wiedmeyer, Ray H.; Brown, L.D.; Casteel, S.W.

    1999-01-01

    In the United States lead is an ubiquitous environmental pollutant that is a serious human health hazard, especially for women of childbearing age, developing fetuses, and young children. Information concerning the uptake and distribution of lead to maternal and fetal tissues during pregnancy is poorly documented. A study was designed using domestic swine and lead isotope enrichment methodology to focus on maternal absorption and distribution of lead into bone and soft tissues, including the fetal compartment, under varying conditions of oral lead exposure and during altered physiological states (pregnant vs unbred). Total lead levels and Pb207/Pb206 ratios in bone (femur and vertebra), blood, and soft tissues (liver, kidney, brain) were determined by ICP-MS. Lead in fetal tissues derived from maternal bone could be differentiated from that derived from exogenous dosing. Unbred swine absorbed much less lead than pregnant females receiving the same dose. The accuracy and precision of ICP-MS at the instrumental level and for the entire method (sample collection, digestion, and analysis) were evaluated for both Pb207/Pb206 ratios and total lead. Several changes were suggested in method design to improve both instrumental and total method precision.

  15. Detection of Engineered Copper Nanoparticles in Soil Using Single Particle ICP-MS.

    PubMed

    Navratilova, Jana; Praetorius, Antonia; Gondikas, Andreas; Fabienke, Willi; von der Kammer, Frank; Hofmann, Thilo

    2015-12-10

    Regulatory efforts rely on nanometrology for the development and implementation of laws regarding the incorporation of engineered nanomaterials (ENMs) into industrial and consumer products. Copper is currently one of the most common metals used in the constantly developing and expanding sector of nanotechnology. The use of copper nanoparticles in products, such as agricultural biocides, cosmetics and paints, is increasing. Copper based ENMs will eventually be released to the environment through the use and disposal of nano-enabled products, however, the detection of copper ENMs in environmental samples is a challenging task. Single particle inductively coupled plasma mass spectroscopy (spICP-MS) has been suggested as a powerful tool for routine nanometrology efforts. In this work, we apply a spICP-MS method for the detection of engineered copper nanomaterials in colloidal extracts from natural soil samples. Overall, copper nanoparticles were successfully detected in the soil colloidal extracts and the importance of dwell time, background removal, and sample dilution for method optimization and recovery maximization is highlighted.

  16. Detection of Engineered Copper Nanoparticles in Soil Using Single Particle ICP-MS

    PubMed Central

    Navratilova, Jana; Praetorius, Antonia; Gondikas, Andreas; Fabienke, Willi; von der Kammer, Frank; Hofmann, Thilo

    2015-01-01

    Regulatory efforts rely on nanometrology for the development and implementation of laws regarding the incorporation of engineered nanomaterials (ENMs) into industrial and consumer products. Copper is currently one of the most common metals used in the constantly developing and expanding sector of nanotechnology. The use of copper nanoparticles in products, such as agricultural biocides, cosmetics and paints, is increasing. Copper based ENMs will eventually be released to the environment through the use and disposal of nano-enabled products, however, the detection of copper ENMs in environmental samples is a challenging task. Single particle inductively coupled plasma mass spectroscopy (spICP-MS) has been suggested as a powerful tool for routine nanometrology efforts. In this work, we apply a spICP-MS method for the detection of engineered copper nanomaterials in colloidal extracts from natural soil samples. Overall, copper nanoparticles were successfully detected in the soil colloidal extracts and the importance of dwell time, background removal, and sample dilution for method optimization and recovery maximization is highlighted. PMID:26690460

  17. Determination of trace elements in rat organs implanted with endodontic repair materials by ICP-MS.

    PubMed

    Simsek, Neslihan; Bulut, Elçin Tekin; Ahmetoğlu, Fuat; Alan, Hilal

    2016-03-01

    To investigate the levels of seven elements using an inductively coupled plasma-mass spectrometry (ICP-MS) method in rat organs after the implantation of Micro Mega Mineral Trioxide Aggregate (MM-MTA), Bioaggregate (BA) and Biodentine (BD) materials. MM-MTA, BA and BD were implanted into the subcutaneous tissue of 15 Wistar albino rats; three control animals had no operation. After 45 days, the rats were sacrificed and their brains, kidneys and livers were removed. The ICP-MS analysis was used to determine trace elements. Data were analysed using the Kruskal-Wallis and Connover post hoc tests. There was no significant difference between the control groups and the MM-MTA, BA and BD groups according to the concentration of aluminum, calcium, arsenic and lead in the rats' organs. Beryllium was not detected in all tissue samples. Chromium levels of these materials were higher than the control group in brain and kidney samples (P = 0.038 and P = 0.037); magnesium levels were higher than the control group in kidney and liver samples (P = 0.030 and P = 0.008). MM-MTA, BA and BD were nontoxic according to trace element levels in brain, kidney and liver samples of rats. Further investigation is required to understand the systemic effects of these materials. PMID:26758893

  18. Standards for Quantitative Metalloproteomic Analysis Using Size Exclusion ICP-MS.

    PubMed

    Lothian, Amber; Roberts, Blaine R

    2016-01-01

    Metals are essential for protein function as cofactors to catalyze chemical reactions. Disruption of metal homeostasis is implicated in a number of diseases including Alzheimer's and Parkinson's disease, but the exact role these metals play is yet to be fully elucidated. Identification of metalloproteins encounters many challenges and difficulties. Here we report an approach that allows metalloproteins in complex samples to be quantified. This is achieved using size exclusion chromatography coupled with inductively coupled plasma - mass spectrometry (SEC-ICP-MS). Using six known metalloproteins, the size exclusion column can be calibrated and the respective trace elements (iron, copper, zinc, cobalt, iodine) can be used for quantification. SEC-ICP-MS traces of human brain and plasma are presented. The use of these metalloprotein standards provides the means to quantitatively compare metalloprotein abundances between biological samples. This technique is poised to help shed light on the role of metalloproteins in neurodegenerative disease as well as other diseases where imbalances in trace elements are implicated. PMID:27167680

  19. Standards for Quantitative Metalloproteomic Analysis Using Size Exclusion ICP-MS

    PubMed Central

    Lothian, Amber; Roberts, Blaine R.

    2016-01-01

    Metals are essential for protein function as cofactors to catalyze chemical reactions. Disruption of metal homeostasis is implicated in a number of diseases including Alzheimer's and Parkinson's disease, but the exact role these metals play is yet to be fully elucidated. Identification of metalloproteins encounters many challenges and difficulties. Here we report an approach that allows metalloproteins in complex samples to be quantified. This is achieved using size exclusion chromatography coupled with inductively coupled plasma - mass spectrometry (SEC-ICP-MS). Using six known metalloproteins, the size exclusion column can be calibrated and the respective trace elements (iron, copper, zinc, cobalt, iodine) can be used for quantification. SEC-ICP-MS traces of human brain and plasma are presented. The use of these metalloprotein standards provides the means to quantitatively compare metalloprotein abundances between biological samples. This technique is poised to help shed light on the role of metalloproteins in neurodegenerative disease as well as other diseases where imbalances in trace elements are implicated. PMID:27167680

  20. [Determination of 27 elements in Maca nationality's medicine by microwave digestion ICP-MS].

    PubMed

    Yu, Gui-fang; Zhong, Hai-jie; Hu, Jun-hua; Wang, Jing; Huang, Wen-zhe; Wang, Zhen-zhong; Xiao, Wei

    2015-12-01

    An analysis method has been established to test 27 elements (Li, Be, B, Mg, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Sr, Mo, Cd, Sn, Sb, Ba, La, Hg, Pb, Bi) in Maca nationality's medicine with microwave digestion-ICP-MS. Sample solutions were analyzed by ICP-MS after microwave digestion, and the contents of elements were calculated according to their calibration curves, and internal standard method was adopted to reduce matrix effect and other interference effects. The experimental results showed that the linear relations of all the elements were very good; the correlation coefficient (r) was 0.9994-1.0000 (Hg was 0.9982) ; the limits of detection were 0.003-2.662 microg x L(-1); the relative standard deviations for all elements of reproducibility were lower than 5% (except the individual elements); the recovery rate were 78.5%-123.7% with RSD lower than 5% ( except the individual elements). The analytical results of standard material showed acceptable agreement with the certified values. This method was applicable to determinate the contents of multi-elements in Maca which had a high sensitivity, good specificity and good repeatability, and provide basis for the quality control of Maca.

  1. The mineralization age of the Makeng Fe deposit, South China: implications from U-Pb and Sm-Nd geochronology

    NASA Astrophysics Data System (ADS)

    Zhang, Zhenjie; Zuo, Renguang; Cheng, Qiuming

    2015-04-01

    The Makeng Fe deposit is located in the southwestern Fujian district, South China. The Sm-Nd isochron ages of seven samples of pure garnet and five of pure magnetite separates from the Makeng ores yielded an isochron age of 157 ± 15 Ma. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) zircon U-Pb dating of the nearby exposed the Dayang-Juzhou (DJ) porphyritic biotite granite and fine-grained syenogranite yielded 206Pb/238U ages of 140.2 ± 1.1 and 140.1 ± 1.0 Ma, respectively. These results suggest that the intrusion of the DJ granite and the Makeng skarn alterations and Fe mineralization are contemporaneous. The DJ granite exhibits geochemical characteristics of A-type granites, including high values of Na2O + K2O (8.13-8.92 wt%), FeOt/MgO (3.4-21.5), and Ga/Al (2.64-3.45 × 10-4), and low Al2O3 (10.71-13.29 wt%) value. Chondrite-normalized rare earth element patterns are characterized by obviously negative Eu anomalies (δEu = 0.02-0.28) and primitive-mantle normalized spidergrams show the enrichment in high field strength element and depleting in Sr, Ti, Ba, and Eu. The geochemical characteristics of DJ granite suggest that the granite was derived from partial melting of the Paleoproterozoic metasedimentary rocks of the Cathaysia basement. And some underplating of mafic magma in the lower tholeiitic crust and/or depleted mantle might be involved and provide the heat source for the partial melting. The DJ granite also fits the spatiotemporal distribution of the Jurassic-Cretaceous coastward migration of both extensional and arc-related magmatism and fills the A-type granites gap in the early stage of the early Cretaceous (145-125 Ma). Therefore, it is suggested that the late Jurassic and early Cretaceous magmatism in southwestern Fujian district were generated in an extensional environment responding to the slab rollback and concomitant retreating arc system of the paleo-Pacific plate within the South China Block. And the Fe metallogeny

  2. Reduction of Solvent Effect in Reverse Phase Gradient Elution LC-ICP-MS

    SciTech Connect

    Sullivan, Patrick Allen

    2005-12-17

    Quantification in liquid chromatography (LC) is becoming very important as more researchers are using LC, not as an analytical tool itself, but as a sample introduction system for other analytical instruments. The ability of LC instrumentation to quickly separate a wide variety of compounds makes it ideal for analysis of complex mixtures. For elemental speciation, LC is joined with inductively coupled plasma mass spectrometry (ICP-MS) to separate and detect metal-containing, organic compounds in complex mixtures, such as biological samples. Often, the solvent gradients required to perform complex separations will cause matrix effects within the plasma. This limits the sensitivity of the ICP-MS and the quantification methods available for use in such analyses. Traditionally, isotope dilution has been the method of choice for LC-ICP-MS quantification. The use of naturally abundant isotopes of a single element in quantification corrects for most of the effects that LC solvent gradients produce within the plasma. However, not all elements of interest in speciation studies have multiple naturally occurring isotopes; and polyatomic interferences for a given isotope can develop within the plasma, depending on the solvent matrix. This is the case for reverse phase LC separations, where increasing amounts of organic solvent are required. For such separations, an alternative to isotope dilution for quantification would be is needed. To this end, a new method was developed using the Apex-Q desolvation system (ESI, Omaha, NE) to couple LC instrumentation with an ICP-MS device. The desolvation power of the system allowed greater concentrations of methanol to be introduced to the plasma prior to destabilization than with direct methanol injection into the plasma. Studies were performed, using simulated and actual linear methanol gradients, to find analyte-internal standard (AIS) pairs whose ratio remains consistent (deviations {+-} 10%) over methanol concentration ranges of 5

  3. Chemical and U-Pb dating investigation of zircons from alnöites on Malaita, Solomon Islands: evidence for prolonged kimberlite-type magmatic activity

    NASA Astrophysics Data System (ADS)

    Simonetti, A.; Neal, C. R.

    2009-12-01

    The Solomon Islands chain is located in an area dominated by the Ontong Java Plateau (OJP). The island of Malaita formed at the obducted leading edge of the OJP and is geologically distinct from the islands to the west. Occurrences of pipe-like bodies of alnöite outcrop within limestones and mudstones in northern Malaita and have been seismically imaged offshore within the OJP. The Malaita alnöite is silica-undersaturated and contains a rich and varied suite of peridotite xenoliths and megacrysts (clinopyroxene, garnet, ilmenite, phlogopite, and minor zircon). The alnöite and associated megacrysts have been the focus of detailed chemical and radiogenic isotope investigations but the exact age of alnöite emplacement remains debatable. Previously reported ages for minerals associated with the Malaita alnöites include an Ar-Ar date of 34 Ma for phlogopite from a mantle xenolith, and a single 206Pb/238U date of 33.9 Ma obtained from a single zircon megacryst. Here we report on a detailed chemical (major and trace element) and U-Pb age investigation of zircon crystals recovered from rivers in the Aluta, Kwainale, and Faufaumela regions of central Malaita. The major element (SiO2, ZrO2, and HfO2) composition and back scattered electron (BSE) imaging of mm- to cm-sized zircons from the three locations were conducted by electron microprobe analysis. The data reveal a variation in the Zr/Hf ratio (45 to 57) for zircons from the Aluta area, whereas this ratio is relatively uniform in most zircons from Kwainale (Zr/Hf 45 to 48). Of importance, the BSE imaging reveals the homogeneous nature of the grains and the lack of inherited components. Trace element compositions of the zircon crystals were obtained by laser ablation (LA)-ICP-MS and these reveal similar chondrite-normalized REE patterns at variable enrichment levels for all grains analyzed; these patterns along with the U, Th, and Pb contents are similar to those documented for mantle-derived zircons formed within

  4. LIMA U-Pb ages link lithospheric mantle metasomatism to Karoo magmatism beneath the Kimberley region, South Africa

    NASA Astrophysics Data System (ADS)

    Giuliani, Andrea; Phillips, David; Maas, Roland; Woodhead, Jon D.; Kendrick, Mark A.; Greig, Alan; Armstrong, Richard A.; Chew, David; Kamenetsky, Vadim S.; Fiorentini, Marco L.

    2014-09-01

    The Karoo igneous rocks (174-185 Ma) of southern Africa represent one of the largest continental flood basalt provinces on Earth. Available evidence indicates that Karoo magmas either originated in the asthenosphere and were extensively modified by interaction with the lithospheric mantle prior to emplacement in the upper crust; or were produced by partial melting of enriched mantle lithosphere. However, no direct evidence of interaction by Karoo melts (or their precursors) with lithospheric mantle rocks has yet been identified in the suites of mantle xenoliths sampled by post-Karoo kimberlites in southern Africa. Here we report U-Pb ages for lindsleyite-mathiasite (LIMA) titanate minerals (crichtonite series) from three metasomatised, phlogopite and clinopyroxene-rich peridotite xenoliths from the ∼84 Ma Bultfontein kimberlite (Kimberley, South Africa), located in the southern part of the Karoo magmatic province. The LIMA minerals appear to have formed during metasomatism of the lithospheric mantle by fluids enriched in HFSE (Ti, Zr, Hf, Nb), LILE (K, Ba, Ca, Sr) and LREE. LIMA U-Pb elemental and isotopic compositions were measured in situ by LA-ICP-MS methods, and potential matrix effects were evaluated by solution-mode analysis of mineral separates. LIMA minerals from the three samples yielded apparent U-Pb ages of 177±12 Ma, 178±29 Ma and 190±24 Ma (±2σ). A single zircon grain extracted from the ∼190 Ma LIMA-bearing sample produced a similar U-Pb age of 184±6 Ma, within uncertainty of the LIMA ages. These data provide the first robust evidence of fluid enrichment in the lithospheric mantle beneath the Kimberley region at ∼180-190 Ma, and suggest causation of mantle metasomatism by Karoo melts or their precursor(s). The results further indicate that U-Pb dating of LIMA minerals provides a new, accurate tool for dating metasomatic events in the lithospheric mantle.

  5. Laser Ablation Analyses of Pb Isotopes in Ancient Feldspars: Application to a Polymetamorphic Terrane, West Greenland

    NASA Astrophysics Data System (ADS)

    Krogstad, E. J.; Baker, J. A.; Waight, T. E.

    2001-12-01

    Laser ablation was used to sample the Pb isotopic compositions of various feldspars, as well as isotopic standards. The ablated material was analyzed by MC-ICP-MS. The resulting accuracy and external precision are comparable to conventional (i.e., not double or triple-spiked) feldspar Pb isotope analyses done by TIMS. However, the data can be acquired with no chemical separation and require only a few minutes per sample. A pilot study was made of the feldspars from a polymetamorphic terrane in West Greenland, in which Late Archean gneisses were deformed and metamorphosed during the Early Proterozoic. In this terrane, isotopic contrasts have long been sought to delineate any suture between discrete Archean continental blocks that might mark the site of ocean closure. Previous whole rock Nd and Pb isotopic studies had yielded equivocal results on the presence of such an isotopic discontinuity. The laser ablation feldspar data presented here, combined with existing whole rock Pb data, point to real differences in the sources of gneisses from various parts of the orogen. This indicates that the laser ablation method of sampling feldspar Pb holds real potential for future reconnaissance studies of old continental crust in a manner similar to that of zircon U-Pb geochronology studies.

  6. Epigenetics: an important challenge for ICP-MS in metallomics studies.

    PubMed

    Wrobel, Katarzyna; Wrobel, Kazimierz; Caruso, Joseph A

    2009-01-01

    Trace metal analysis has been long regarded as one of the principle tasks in areas of chemical analysis. At the early stage of instrumental development, total concentration was assessed in a variety of samples, yielding results, among others, for environmental, biological, and clinical samples. With the power of newer analytical techniques, such as inductively coupled plasma mass spectrometry (ICP-MS), accurate quantitative results can now be obtained at ultra-trace levels not only for metals, but also for metalloids and several non-metals. Even though the importance of trace elements in many biological processes is widely accepted, the elucidation of their biological pathways, understanding specific biological functions, or possible toxicological aspects is still a challenge and a driving force to further develop analytical methodology. Over the past decades, the scientific interest has moved from total element determination to include speciation analysis, which provides quantitative information of one or more individual element species in a sample. More recently, metallomics has been introduced as a more expanded concept, in which the global role of all metal/metalloids in a given system is considered. Owing to the multi-elemental focus of metallomics research, the use of ICP-MS becomes indispensable. Furthermore, considering the biological role of metals/metalloids and the use of elements as internal or external molecular tags, epigenetics should be considered as an important emerging application for metallomics studies and approaches. Among a variety of epigenetic factors, essential nutrients, but also environmental toxins, have been shown to affect DNA methylation, modification of histone proteins, and RNA interference, all of them being implicated in cancer, cardiovascular disease, and several inherited conditions. Recent studies suggest that epigenetics may be a critical pathway by which metals produce health effects. In this Trends article, the basic

  7. Precise and Sensitive Lithium Isotope Ratios by Quadrupole ICP-MS

    NASA Astrophysics Data System (ADS)

    Misra, S.; Froelich, P. N.

    2008-05-01

    We present a new method for the determination of 7Li/6Li with low Li consumption (<0.3 ng/analysis), high column yields (>99.99%), high Isotope Ratio precision (< ±0.9‰, 2σ), and low blank (<500 fg/ml). We optimize for analyses of natural carbonates (foraminifera) containing 1-2 ppm-Li. Measurements are done with a single collector Quadrupole ICP-MS (Agilent 7500cs) using cold plasma (600W) to eliminate doubly-charged 12C2+ and 14N2+, soft extraction to maximize and stabilize the Li-signal, peak jumping and pulse detection of both Li isotopes, with Standard-Sample-Standard bracketing. Li solutions of 0.2 to 0.4 ppb concentration were analyzed using PFA micro-concentric nebulizer (uptake rate = 200μl/min) for a period of ~3 min/sample. The long-term external precision is ±0.9‰ (2σ) for LSVEC Li standards and ±1.5‰ (2σ) for forams, comparable to MC-ICP-MS methods. The key improvement of our method is the small Li-mass requirement (<0.3 ng/quintuplicate) compared to other ICP- MS methods (3-40 ng/analysis). Li isotope measurements in forams are limited not only by low Li concentrations but also by instrument-induced fractionation effects, matrix effects and incomplete column recovery and fractionation of Li during column separations to remove alkali and alkaline earth elements. Column separations remove these ions but induce potentially large Li-isotope fractionation in elution peaks, from +100‰ in the leading edge (ca. 1% Li load) to -100‰ in the trailing edge (ca. 1% Li load). Thus tiny incomplete Li- recoveries during column separations can result in large unrecognized column-induced fractionation of eluted Li. These factors conspire to require a column method with both 100% recovery and quantitative separation of matrix elements. We refined a single step ion chromatographic method to quantitatively recover (>99.99% yield) and separate Li from all matrix elements using small volume resin (2ml / 3.4meq AG50W-X8) and low elution volume (6ml of 0.5N

  8. Analysis of Provenance of Siwalik Group in Western Nepal Himalaya Using Petrography and U-Pb Geochronology

    NASA Astrophysics Data System (ADS)

    Baral, U.; Lin, D.; Chamlagain, D.

    2014-12-01

    The east-west trending southernmost litho-tectonic unit, Siwalik, is about 5 Km thick fluvial coarsening upward sequence, which was deposited during middle Miocene to early Pleistocene. This fluvial sediment is excellent archives of the Himalayan exhumation, tectonic events and mountain building processes. This paper deals with the possible provenance of the middle Miocene to early Pleistocene fluvial sediments along the Karnali River section as well as added some knowledge of the Himalayan orogeny by the means of petrography and detrital zircon U-Pb dating under LA-ICP-MS. The petrographic studies shows the detritus grain of sandstones from the Karnali River section falls on 'recycled orogeny' field on QFL plots. The detrital zircon U-Pb geochronological study shows that the sediments were mostly derived from entire three litho units ;Tethys, Higher, and Lesser Himalaya during the time of deposition of Siwalik whereas the erosion process of Lesser Himalayan sediment increased after ~10 Ma. Overall, the combined studies show the mixed type of provenance as seen in the western Himalaya of India. Key words: U-Pb geochronology, Provenance, Siwalik Group

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

    USGS Publications Warehouse

    May, T.W.; Wiedmeyer, Ray H.; Brumbaugh, W.G.; Schmitt, C.J.

    1997-01-01

    Concentrations of metals in sediment interstitial water (pore water) and those extractable from sediment with weak acids can provide important information about the bioavailability and toxicological effects of such contaminants. The highly variable nature of metal concentrations in these matrices requires instrumentation with the detection limit capability of graphite furnace atomic absorption and the wide dynamic linear range capability of ICP-OES. These criteria are satisfied with ICP-MS instrumentation. We investigated the performance of ICP-MS in the determination of certain metals from these matrices. The results for three metals were compared to those determined by graphite furnace atomic absorption spectroscopy. It was concluded that ICP-MS was an excellent instrumental approach for the determination of metals in these matrices.

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

    PubMed

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

    2016-07-01

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

  11. Identification of a matrix effect in the MC-ICP-MS due to sample purification using ion exchange resin

    NASA Astrophysics Data System (ADS)

    Pietruszka, Aaron J.; Reznik, Audrey D.

    2008-02-01

    Multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has become the preferred method for precise and accurate measurements of the relative abundances of many radiogenic and stable isotopes in natural materials. Isotopic analyses by MC-ICP-MS require a correction for instrumental mass-dependent isotopic fractionation ("instrumental mass bias"). Two techniques have been used to correct for instrumental mass bias in the MC-ICP-MS: (1) standard-sample bracketing (SSB) or (2) double spiking. SSB is often cited as the preferred method, but it is more susceptible to matrix effects. Here we demonstrate that a matrix effect in the MC-ICP-MS may arise indirectly from the chemical separation and purification of molybdenum using anion exchange resin. The results of our experiments show that a Mo standard passed through a column of anion exchange resin or a Mo standard added to a Mo-free solution that had been collected from anion exchange resin appears to be isotopically lighter than expected from direct analysis of the same standard. Using amounts of Mo similar to what might be expected from most natural samples (~3 [mu]g per column cut), these offsets span a significant fraction (~10-60%) of the total known range of mass-dependent Mo isotopic variation in nature. This "column matrix effect" appears to be caused by organic material stripped from the resin. All of our attempts to eliminate or control this column matrix effect have failed, making it difficult (if not impossible) to obtain accurate measurements of mass-dependent Mo isotopic variations in natural materials using the anion exchange resin procedure described in this study and SSB techniques to correct for instrumental mass bias in the MC-ICP-MS. It is currently unknown if this type of column matrix effect will affect measurements of other stable or radiogenic isotopes by MC-ICP-MS when SSB is used to correct for instrumental mass bias.

  12. Elemental speciation in biomolecules by LC-ICP-MS with magnetic sector and collision cell instruments

    SciTech Connect

    Wang, Jin

    1999-11-08

    A methodology that can monitor and identify inorganic elements in biological and environmental systems was developed. Size exclusion chromatography (SEC) separates biomolecules, which are then nebulized by a microconcentric nebulizer. The resulting aerosol is desolved and introduced into either a high resolution ICP-MS device or a quadrupole device with a collision cell. Because of the high sensitivity and spectral resolution and high sample introduction efficiency, many unusual or difficult elements, such as Cr, Se, Cd and U, can be observed at ambient levels bound to proteins in human serum. These measurements are made in only a few minutes without preliminary isolation and preconcentration steps. Serum samples can be titrated with spikes of various elements to determine which proteins bind a given metal and oxidation state. Experiments concerning the effects of breaking disulfide linkages and denaturation on metal binding in proteins were also investigated. Elemental distribution in liver extract was also obtained.

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

    NASA Astrophysics Data System (ADS)

    Voica, Cezara; Kovacs, Melinda; Feher, Ioana

    2013-11-01

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

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

    SciTech Connect

    Voica, Cezara Kovacs, Melinda Feher, Ioana

    2013-11-13

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

  15. Evaluation of chelation preconcentration for the determination of actinide elements by flow injection ICP-MS

    SciTech Connect

    Evans, E.H.; Truscott, J.B.; Bromley, L.; Jones, P.; Turner, J.; Fairman, B.E.

    1998-12-31

    A chelation column preconcentration method has been developed for the determination of uranium and thorium in waters by ICP-MS. Detection limits of 24 pg and 60 pg respectively were obtained, but these were blank limited. Uranium and Thorium were determined in certified reference materials. Results for uranium were 121 {+-} 21 and 15 {+-} 3 ng/g in NIST 1566a and NIST 1575 compared with certified values of 132 {+-} 12 and 20 {+-} 4 ng/g respectively. Results for thorium were 29 {+-} 8 and 28 {+-} 5 ng/g in NIST 1566a and NIST 1575 compared with indicative and certified values of 40 and 37 {+-} 3 ng/g respectively. The on-line separation of actinide radionuclides was achieved by selective elution of U, Th, Pu, Np, and Am.

  16. The Approach to Reducing the Detection Limit for LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Poteshin, S. S.; Sysoev, Alexey A.; Torbotryas, R.

    This work is a part of the RED-100 big project. The aim of the RED-100 experiment is to detect the presently undiscovered coherent neutrino scattering off xenon atomic nuclei. The manufacture of such detectors requires ultrapure materials with very low content of natural radioactive elements. So the pure titanium was selected to assay the uranium and thorium contaminations on 1 ng/g level. In this paper we investigate the possibility of reducing the LOD for LA-ICP-MS analysis by increasing the pulse repetition rate of solid-state laser irradiation up to 4,000 Hz and appropriate adjusting the irradiation power. LODs for U and Th in titanium matrix estimation fell in the sub 10-10 g g- 1 level.

  17. [Application of ICP-MS to the detection of heavy metals in transgenic corn].

    PubMed

    Rui, Yu-Kui; Guo, Jing; Huang, Kun-Lun; Jin, Yin-Hua; Luo, Yun-Bo

    2007-04-01

    With the rapid development of the transgenic food, more and more transgenic food has been pouring into the market attracting much attention to the transgenic food's edible safety. Transgenic corns and its parents were studied by ICP-MS to detect the heavy metals. The results showed that the transgenic corn accumulated less heavy metals (Ni, Cu, Cd, As, Cr, Zn and Hg) than their own parents; and the contents of some heavy metals (V, Co and Pb) in transgenic corns were similar to their parents. All the data showed that the insertion of foreign gene (Bt) might change the absorbing dynamics of most heavy metals, especially some important heavy metals, which are disadvantageous to human health. The present paper indicated that the change in heavy metals absorption could harm the edible safety of transgenic plant. The cause of this change should be studied further.

  18. [Application of ICP-MS to the detection of 22 elements in transgenic soybean oil].

    PubMed

    Wel, Zhen-lin; Shen, Lin; Rui, Yu-kui; Jiao, Chuan-zhen

    2008-06-01

    With the rapid development of transgenic food, more and more transgenic food has been pouring into the market, and much attention has been paid to the edible safety of transgenic food. Transgenic soybean oils were studied by ICP-MS to detect 22 kinds of elements. The results showed that the contents of 7 kinds of macroelements range from 0. 13 to 12.52 microg x g(-1) in transgenic soybean oils, the range of the rest 15 kinds of microelements is from 0.15 ng x g(-1) to 7)0.00 ng x g(-1). The sequence of macroelement concentration is Ca>Na>K>Mg>Al>P>Si. There are 5 kinds of micoelements whose concentrations were higher than 200 ng x g(-1), including Zn>Ba>Cr>Fe>Ti, especially Zn, Ba, Cr and Fe.

  19. Determination of 241Pu in nuclear waste slurries: a comparative study using LSC and ICP-MS.

    PubMed

    Jäggi, M; Röllin, S; Alvarado, J A Corcho; Eikenberg, J

    2012-02-01

    (241)Pu was determined in slurry samples from a nuclear reactor decommissioning project at the Paul Scherrer Institute (Switzerland). To validate the results, the (241)Pu activities of five samples were determined by LSC (TriCarb and Quantulus) and ICP-MS, with each instrument at a different laboratory. In lack of certified reference materials for (241)Pu, the methods were further validated using the (241)Pu information values of two reference sediments (IAEA-300 and IAEA-384). Excellent agreement with the results was found between LSC and ICP-MS in the nuclear waste slurries and the reference sediments.

  20. Determination of 241Pu in nuclear waste slurries: a comparative study using LSC and ICP-MS.

    PubMed

    Jäggi, M; Röllin, S; Alvarado, J A Corcho; Eikenberg, J

    2012-02-01

    (241)Pu was determined in slurry samples from a nuclear reactor decommissioning project at the Paul Scherrer Institute (Switzerland). To validate the results, the (241)Pu activities of five samples were determined by LSC (TriCarb and Quantulus) and ICP-MS, with each instrument at a different laboratory. In lack of certified reference materials for (241)Pu, the methods were further validated using the (241)Pu information values of two reference sediments (IAEA-300 and IAEA-384). Excellent agreement with the results was found between LSC and ICP-MS in the nuclear waste slurries and the reference sediments. PMID:22079960

  1. Complementary Use of LC-ICP-MS and LC-ESI-Q-TOF-MS for Selenium Speciation.

    PubMed

    Anan, Yasumi; Nakajima, Genki; Ogra, Yasumitsu

    2015-01-01

    We demonstrated the complementary use of inductively coupled plasma-mass spectrometry (ICP-MS) and electrospray ionization quadrupole time-of-flight mass spectrometry (ESI-Q-TOF-MS) for the analysis of Se-containing compounds, such as selenate, selenomethionine (SeMet), and trimethylselenonium ion (TMSe), found in biological samples. The sensitivity of ESI-Q-TOF-MS for Se-containing compounds was strongly dependent on the chemical species. ICP-MS exhibited higher sensitivity than ESI-Q-TOF-MS, and had no species dependency. On the other hand, ESI-Q-TOF-MS enabled easy and robust identification of Se-containing compounds.

  2. Fingerprinting of ground water by ICP-MS. Progress report, January 1, 1995--March 31, 1995

    SciTech Connect

    Stetzenbach, K.

    1995-05-01

    This report contains the results of the chemical analysis of water from springs in Ash Meadows National Wildlife Refuge, Nevada. Each spring was sampled two to five times between July, 1992 and March, 1994. Samples were collected and analyzed by the Harry Reid Center for Environmental Studies (HRC) Environmental/Analytical Laboratory, at the University of Nevada, Las Vegas. Chemical analyses included major cations and anions and trace elements. The analyses for the major anions were performed by atomic absorption (AA) spectrophotometry, the anions by ion chromatography (IC) and the trace elements by inductively coupled plasma - mass spectrometry (ICP-MS). The standard operating procedures (SOP) used for each method are included. The concentrations of the analytes range from the part per million (ppm) levels for the major cations and anions to the sub part per trillion (ppt) levels for a number of the trace elements. Approximately nine orders of magnitude are covered from the highest to the lowest concentrations. The formation of molecular species in the ICP-MS, plasma produces false positives for a number of elements. None of the elements reported here, that the HRC is aware of, are subject to these isobaric interferences, with the exception of europium (Eu). Europium values are reported for samplings four and five where the HRC used an extraction procedure that extracted Eu but not barium (Ba), whose oxides cause the interference. In order to overcome matrix effects in the samples from high concentrations of cations and other elements, the method of standard additions was instituted for the analysis of samplings four and five as an alternative to external standardization. It is believed that these data, and those for the Death Valley Spring reported in January, 1995 are the first efforts at such a comprehensive trace element analysis of ground waters. HRC has had to develop, test, and refine sampling and analysis procedures throughout the course of this study.

  3. [Analysis of different types of soil by FTIR and ICP-MS].

    PubMed

    Zhao, Shuai-qun; Liu, Gang; Ou, Quan-hong; Xu, Juan; Ren, Jing; Hao, Jian-ming

    2014-12-01

    Fourier transform infrared spectroscopy (FTIR) and inductively coupled plasma mass spectrometry (ICP-MS) were used to study six types of farmland soil from different areas. The FTIR results showed that the infrared spectra of soil were mainly composed of the absorption band of clay minerals, organic matter and inorganic salts, such as carbonate, phosphate, manganate and so on. The mineral atlas of six soil samples were all of montmorillonite type. The ICP-MS test results showed that the available elements content of different types and colours of soil samples were different There was significant lack status of available Ca between different types of farmland soil, the content of available Mg in Huludao soil was in the medium level, other areas were in the status of shortage. There was only significant lack status of available Mn and available Zn in Baiyin soil, the content of available Fe in Chenggong soil was in the status of shortage, the content of available Cu in all areas was particularly rich. The content of available P in Jining soil was rich, Luoyang and Huludao soil were in the medium level, the soil of Chenggong, Baiyin and Luliang were in the status of shortage. The content of available K in Luoyang, Chenggong and Jining soil was relatively rich, Luliang soil was in the medium level, the soil of Huludao and Baiyin were in the status of shortage. It is observed that the deeper the color of soil samples, the richer the amount of some available trace elements such as magnesium, copper, iron, manganese and zinc. According to the national classification standard of available elements content, we analyzed the nutrients of available elements content in the farmland soil of different areas, and implemented remedial measures for the lacking of available elements for all of the six areas.

  4. Direct determination of gold in rock samples using collision cell quadrupole ICP-MS.

    PubMed

    Yim, Seong A; Choi, Man Sik; Chae, Jung Sun

    2012-01-01

    This study investigated the determination of Au in rock samples using collision cell quadrupole inductively coupled plasma mass spectrometry (ICP-MS). It is essential to remove various interferents using a collision cell because polyatomic ions such as (181)Ta(16)O(+) and (180)Hf(16)O(1)H(+) can interfere with the direct determination of monoisotopic (197)Au when using ICP-MS. The addition of oxygen as a reaction gas removed isobaric interferents by transforming TaO(+) and HfOH(+) to TaO(2)(+), TaO(3)(+), and HfO(2)H(+), HfO(3)H(+), respectively, in the cell without significant Au(+) loss. The ion kinetic energy effect (IKEE) due to the potential difference between the plasma and the hexapole affected the reactions in the cell. Au and interfering ions were very sensitive to cell bias voltage (Vc) at constant plasma potential (Vp) and quadrupole bias voltage (Vq). Under the condition of hot plasma, the transmission of ions was promoted, and the maximum Au signal intensity was 50% greater than under normal conditions. At Vc > 7 V, TaO(+) ions were removed to background level. Optimized conditions for real sample analysis were obtained by introducing He as an additional collision gas in hot plasma. TaO(+) ions were removed to background level at He flow rates above 0.6 mL min(-1), and the Au signal remained high. The detection limit (three times the standard deviation of the blank) of this method was 3.06 pg g(-1). The results for reference materials (STM-1 and DGPM-1) and spiked samples showed good agreement between specified and measured concentrations.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  6. U-Pb Ages of Lunar Apatites

    NASA Technical Reports Server (NTRS)

    Vaughan, J.; Nemchin, A. A.; Pidgeon, R. T.; Meyer, Charles

    2006-01-01

    Apatite is one of the minerals that is rarely utilized in U-Pb geochronology, compared to some other U-rich accessory phases. Relatively low U concentration, commonly high proportion of common Pb and low closure temperature of U-Pb system of apatite inhibit its application as geochronological tool when other minerals such as zircon are widely available. However, zircon appear to be restricted to certain type of lunar rocks, carrying so called KREEP signature, whereas apatite (and whitlockite) is a common accessory mineral in the lunar samples. Therefore, utilizing apatite for lunar chronology may increase the pool of rocks that are available for U-Pb dating. The low stability of U-Pb systematics of apatite may also result in the resetting of the system during meteoritic bombardment, in which case apatite may provide an additional tool for the study of the impact history of the Moon. In order to investigate these possibilities, we have analysed apatites and zircons from two breccia samples collected during the Apollo 14 mission. Both samples were collected within the Fra Mauro formation, which is interpreted as a material ejected during the impact that formed the Imbrium Basin.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  8. Engineering cyber infrastructure for U-Pb geochronology: Tripoli and U-Pb_Redux

    NASA Astrophysics Data System (ADS)

    Bowring, J. F.; McLean, N. M.; Bowring, S. A.

    2011-06-01

    In the past decade, major advancements in precision and accuracy of U-Pb geochronology, which stem from improved sample pretreatment and refined measurement techniques, have revealed previously unresolvable discrepancies among analyses from different laboratories. One solution to evaluating and resolving many of these discrepancies is the adoption of a common software platform that standardizes data-processing protocols, enabling robust interlaboratory comparisons. We present the results of a collaboration to develop cyber infrastructure for high-precision U-Pb geochronology based on analyzing accessory minerals by isotope dilution-thermal ionization mass spectrometry. This cyber infrastructure implements an architecture specifying the workflows of data acquisition, statistical filtering, analysis and interpretation, publication, community-based archiving, and the compilation and comparison of data from different laboratories. The backbone of the cyber infrastructure consists of two open-source software programs: Tripoli and U-Pb_Redux. Tripoli interfaces with commercially available mass spectrometers using standardized protocols, statistical filtering, and interactive visualizations to aid the analyst in preparing raw data for analysis in U-Pb_Redux. U-Pb_Redux implements the architecture by orchestrating the analyst's workflow with interactive visualizations and provides data reduction and uncertainty propagation that support data interpretations. Finally, U-Pb_Redux enables production of publication-ready graphics and data tables, the archiving of results, and the comparative compilation of archived results to support cooperative science.

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

    NASA Astrophysics Data System (ADS)

    Wildau, Antje; Garbe-Schönberg, Dieter

    2015-04-01

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

  10. Accurate and precise Pb isotope ratio measurements in environmental samples by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Weiss, Dominik J.; Kober, Bernd; Dolgopolova, Alla; Gallagher, Kerry; Spiro, Baruch; Le Roux, Gaël; Mason, Thomas F. D.; Kylander, Malin; Coles, Barry J.

    2004-04-01

    Analytical protocols for accurate and precise Pb isotope ratio determinations in peat, lichen, vegetable, chimney dust, and ore-bearing granites using MC-ICP-MS and their application to environmental studies are presented. Acid dissolution of various matrix types was achieved using high temperature/high pressure microwave and hot plate digestion procedures. The digests were passed through a column packed with EiChrom Sr-resin employing only hydrochloric acid and one column passage. This simplified column chemistry allowed high sample throughput. Typically, internal precisions for approximately 30 ng Pb were below 100 ppm (+/-2[sigma]) on all Pb ratios in all matrices. Thallium was employed to correct for mass discrimination effects and the achieved accuracy was below 80 ppm for all ratios. This involved an optimization procedure for the 205Tl/203Tl ratio using least square fits relative to certified NIST-SRM 981 Pb values. The long-term reproducibility (+/-2[sigma]) for the NIST-SRM 981 Pb standard over a 5-month period (35 measurements) was better than 350 ppm for all ratios. Selected ore-bearing granites were measured with TIMS and MC-ICP-MS and showed good correlation (e.g., r=0.999 for 206Pb/207Pb ratios, slope=0.996, n=13). Mass bias and signal intensities of Tl spiked into natural (after matrix separation) and in synthetic samples did not differ significantly, indicating that any residual components of the complex peat and lichen matrix did not influence mass bias correction. Environmental samples with very different matrices were analyzed during two different studies: (i) lichens, vegetables, and chimney dust around a Cu smelter in the Urals, and (ii) peat samples from an ombrotrophic bog in the Faroe Islands. The presented procedure for sample preparation, mass spectrometry, and data processing tools resulted in accurate and precise Pb isotope data that allowed the reliable differentiation and identification of Pb sources with variations as small as 0

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

    NASA Technical Reports Server (NTRS)

    Smith, Scott M.; Gillman, Patricia L.

    2003-01-01

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

  12. Hydrothermal Zircon U-Pb Dating for Early Cretaceous Iron Skarn Mineralization in the Handan-Xingtai District, North China Craton

    NASA Astrophysics Data System (ADS)

    Deng, X., Sr.; Li, J. W., Sr.; Wen, G., Sr.

    2015-12-01

    The Handan-Xingtai district in the North China craton (NCC) is one of the most important concentrations of iron skarn deposits in China. The iron mineralization occurs predominantly along contact zones between early Cretaceous intrusions and Middle Ordovician marine carbonates. We present textural features and LA-ICP-MS U-Pb dating results of hydrothermal zircon to constrain on the time of iron mineralization. Zircon grains from mineralized skarns are subhedral crystals and euhedral tetragonal bipyramids, which are closely intergrown with skarn minerals. They contain abundant inclusions of skarn minerals and daughter mineral-rich (mostly magnetite, halite, and sylvite) fluid inclusions, and have variable Th (518-17477 ppm) and U (109-25610 ppm) contents, with Th/U ratios of 0.01-5.23. These features indicate their hydrothermal origin. The hydrothermal zircon grains from 5 deposits yield concordant U-Pb ages ranging from 133.6 ± 0.9 to 128.5 ± 1.4 Ma (2σ). These ages are consistent with U-Pb ages (134.1 ± 1.2 to 128.5 ± 0.9 Ma; 2σ) of magmatic zircon grains, confirming the reliability of hydrothermal zircon U-Pb ages. Our new geochronological data indicate that iron mineralization and associated magmatism in the Handan-Xingtai district occurred mainly at the ca. 137-133 and 131-128 Ma intervals. These iron skarn deposits represent as the only known giant Mesozoic iron skarn province in a cratonic block on the Earth. Their formation time coincided with lithospheric thinning or destruction of the NCC, strongly suggesting a causal link between the two processes. Our work provides a valuable approach to date iron skarn mineralization by using U-Pb geochronology of hydrothermal zircon and highlights its potential for similar studies. Keywords: Hydrothermal zircon; LA-ICPMS; U-Pb geochronology, iron skarn deposits; North China craton

  13. Quantitative lead determination in coating paint on children's outwear by LA-ICP-MS: a practical calibration strategy for solid samples.

    PubMed

    Mercan, Selda; Ellez, Sevinç Zeynep; Türkmen, Zeynep; Yayla, Murat; Cengiz, Salih

    2015-01-01

    Lead is a hazardous compound that affects the central nervous system in people, particularly children, and may cause some reversible and irreversible diseases. Legal regulations try to prevent the exposure from products especially produced for children such as coating paints, jewelry, toys, bed linen, textile, etc. The aim of this study was to determine the lead levels of coating paints on children׳s outwear selling in district bazaar by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and to specify the percent of non-complying samples. Here we described the solid matrix calibration method and confirmed the results with the microwave-assisted acid digestion method. Both comparative methods were validated by analysis of the certified reference materials (NIST SRM-612 glass matrix, NIST SRM-2582 powdered paint and ERM-EC681k) and bias% for accuracy and RSD% for precision were calculated lower than 6.8% and 7.3%, respectively. The recovery ranges of laser ablation and microwave-assisted acid digestion method for Pb were found to be between 88.2-98.1% and 95.3-101.3%, respectively. The limits of detection values were determined as 0.162 mg kg(-1) for direct sampling in the ablation chamber and 0.002 ng mL(-1) for aqueous solutions. Correlation result of 16 samples (r=0.99) examined in both methods was satisfactory. In coating paint samples, 14.65% of 198 (n=29) did not comply with the 90 mg kg(-1) lead limit according to regulation. Validated quantitative laser ablation method may be preferred to quickly and reliably determine the Pb levels in other solid samples as well as coating paints.

  14. Determination of Toxic Metals in Little Cigar Tobacco with 'Triple Quad' ICP-MS.

    PubMed

    Pappas, R Steven; Martone, Naudia; Gonzalez-Jimenez, Nathalie; Fresquez, Mark R; Watson, Clifford H

    2015-06-01

    Smoking remains the leading cause of preventable death in the USA. Much of the focus on harmful and potentially harmful constituents (HPHCs) in tobacco products has been on cigarettes. Little cigars gained popularity over the last decade until tobacco taxes made cigarettes more expensive in the USA. Many little cigar brands are similar in size with cigarettes and may be smoked in a similar manner. Scant data are available on HPHC concentrations in little cigars, therefore we developed and applied a new analytical method to determine concentrations of 10 toxic metals in little cigar tobacco. The method utilizes 'triple quadrupole' ICP-MS. By optimizing octapole bias, energy discrimination and cell gas flow settings, we were able to accurately quantify a range of elements including those for which the cell gas reactions were endothermic. All standard modes (Single Quad No Gas, MS-MS NH3/He and MS-MS O2) were utilized for the quantitation of 10 toxic metals in little cigar tobacco, including uranium, which was added as an analyte in the new method. Because of the elimination of interfering ions at 'shifted analyte masses', detection limits were lower compared with a previous method. Tobacco selenium concentrations were below the limit of detection in the previous method, but the new technology made it possible to report all selenium concentrations. PMID:25724197

  15. The Effect of Aqueous Alteration in Antarctic Carbonaceous Chondrites from Comparative ICP-MS Bulk Chemistry

    NASA Technical Reports Server (NTRS)

    Alonso-Azcarate, J.; Trigo-Rodriguez, J. M.; Moyano-Cambero, C. E.; Zolensky, M.

    2014-01-01

    Terrestrial ages of Antarctic carbonaceous chondrites (CC) indicate that these meteorites have been preserved in or on ice for, at least, tens of thousands of years. Due to the porous structure of these chondrites formed by the aggregation of silicate-rich chondrules, refractory inclusions, metal grains, and fine-grained matrix materials, the effect of pervasive terrestrial water is relevant. Our community defends that pristine CC matrices are representing samples of scarcely processed protoplanetary disk materials as they contain stellar grains, but they might also trace parent body processes. It is important to study the effects of terrestrial aqueous alteration in promoting bulk chemistry changes, and creating distinctive alteration minerals. Particularly because it is thought that aqueous alteration has particularly played a key role in some CC groups in modifying primordial bulk chemistry, and homogenizing the isotopic content of fine-grained matrix materials. Fortunately, the mineralogy produced by parent-body and terrestrial aqueous alteration processes is distinctive. With the goal to learn more about terrestrial alteration in Antarctica we are obtaining reflectance spectra of CCs, but also performing ICP-MS bulk chemistry of the different CC groups. A direct comparison with the mean bulk elemental composition of recovered falls might inform us on the effects of terrestrial alteration in finds. With such a goal, in the current work we have analyzed some members representative of CO and CM chondrite groups.

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

    PubMed

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

    2008-03-15

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

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

    PubMed

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

    2005-01-01

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

  18. Profiling and classification of illicit heroin by ICP-MS analysis of inorganic elements.

    PubMed

    Liu, Cuimei; Hua, Zhendong; Bai, Yanping; Liu, Yao

    2014-06-01

    Nineteen inorganic elements (Ag, As, Ba, Cd, Co, Cr, Cu, Mn, Mo, Ni, P, Pb, Se, Sb, Th, Tl, U, V and Zn) in heroin samples were determined using inductive coupled plasma mass spectrometry (ICP-MS). After Wilcoxon-Mann-Whitney test and correlation analysis, 10 element contents (P, V, Cr, Ni, Cu, Zn, As, Se, Pb, U) and 7 element ratios (U/Ba, Ba/Pb, Cd/Mn, Co/Ni, V/Cr, P/V, Cd/V) were found to be evidently different between heroin samples from "Golden Crescent" and "Golden Triangle". Based on the data set of these 17 variables in 150 authentic heroin samples, classification of origins was successfully achieved utilizing principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA). By comparison experiment on 907 unknown samples, the developed discriminant model was proven to be consistent with the widely used organic profiling method, and meanwhile the time consumed per sample was markedly saved, which facilitates high throughput screening in routine analysis.

  19. [Application of ICP-MS to Identify the Botanic Source of Characteristic Honey in South Yunnan].

    PubMed

    Wei, Yue; Chen, Fang; Wang, Yong; Chen, Lan-zhen; Zhang, Xue-wen; Wang, Yan-hui; Wu, Li-ming; Zhou, Qun

    2016-01-01

    By adopting inductively coupled plasma mass spectrometry (ICP-MS) combined with chemometric analysis technology, 23 kinds of minerals in four kinds of characteristic honey derived from Yunnan province were analyzed. The result showed that 21 kinds of mineral elements, namely Na, Mg, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Mo, Cd, Sb, Ba, Tl and Pb, have significant differences among different varieties of honey. The results of principal component analysis (PCA) showed that the cumulative variance contribution rate of the first four main components reached 77.74%, seven kinds of elements (Mg, Ca, Mn, Co, Sr, Cd, Ba) from the first main component contained most of the honey information. Through the stepwise discriminant analysis, seven kinds of elements (Mg, K, Ca, Cr, Mn, Sr, Pb) were filtered. out and used to establish the discriminant function model, and the correct classification rates of the proposed model reached 90% and 86.7%, respectively, which showed elements contents could be effectively indicators to discriminate the four kinds characteristic honey in southern Yunnan Province. In view of all the honey samples were harvested from apiaries located at south Yunnan Province where have similar climate, soil and other environment conditions, the differences of the mineral elements contents for the honey samples mainly due to their corresponding nectariferous plant. Therefore, it is feasible to identify honey botanical source through the differences of mineral elements. PMID:27228779

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

    PubMed Central

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

    2016-01-01

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

  1. Speciation of heavy metals in environmental water by ion chromatography coupled to ICP-MS.

    PubMed

    Ammann, Adrian A

    2002-02-01

    Biogenic (e.g. phytochelatins, porphyrins, DOM) as well as anthropogenic (e.g. NTA, EDTA, phosphonates) chelators affect the mobility and cycling of heavy metals in environmental waters. Since such chelators can form strongly bound anionic heavy metal complexes that are stable and highly mobile, anion-exchange chromatography coupled to ICP-MS was investigated. A narrow bore HPLC system was connected to a micro concentric nebuliser for in-line sample introduction. A new chromatographic procedure based on a synthetic hydrophilic quaternary ammonium anion exchanger in combination with nitrate as a strong eluent anion, and gradient elution, provided high separation selectivity and a large analytical window. Low detection limits (nmol L(-1)) were achieved by on-column matrix removal and sample preconcentration. This allowed the method to be successfully applied to different environmental research areas. In ecotoxicological studies of heavy metal effects on algae low concentrations of metal EDTA complexes were determined in nutrient solutions without interference from high (buffer) salt concentrations. In groundwater, infiltrated by a polluted river, mobile metal EDTA species were observed. In river water of different pollution levels beside CuEDTA other anionic Cu-complexes were found in nmol L(-1) concentrations. PMID:11939532

  2. Uranium levels in Cypriot groundwater samples determined by ICP-MS and α-spectroscopy.

    PubMed

    Charalambous, Chrystalla; Aletrari, Maria; Piera, Panagiota; Nicolaidou-Kanari, Popi; Efstathiou, Maria; Pashalidis, Ioannis

    2013-02-01

    The uranium concentration and the isotopic ratio (238)U/(234)U have been determined in Cypriot groundwater samples by ICP-MS after ultrafiltration and acidification of the samples and α-spectroscopy after pre-concentration and separation of uranium by cation-exchange (Chelex 100 resin) and electro-deposition on stainless steel discs. The uranium concentration in the groundwater samples varies strongly between 0.1 and 40 μg l(-1). The highest uranium concentrations are found in groundwater samples associated with sedimentary rock formations and the obtained isotopic ratio (238)U/(234)U varies between 0.95 and 1.2 indicating basically the presence of natural uranium in the studied samples. The pH of the groundwater samples is neutral to weak alkaline (7 < pH < 8) and this is attributed to the carbonaceous content of the sedimentary rocks and the ophiolitic origin of the igneous rocks, which form the background geology in Cyprus. Generally, in groundwaters uranium concentration in solution increases with decreasing pH (7 < pH < 8) and this is attributed to the fact that at lower pH dissolution of soil minerals occurs, and uranium, which is adsorbed or forms solid solution with the geological matrix enters the aqueous phase. This is also corroborated by the strong correlation between the uranium concentration and the electrical conductivity (e.g. dissolved solids) measured in the groundwaters under investigation.

  3. Uranium levels in Cypriot groundwater samples determined by ICP-MS and α-spectroscopy.

    PubMed

    Charalambous, Chrystalla; Aletrari, Maria; Piera, Panagiota; Nicolaidou-Kanari, Popi; Efstathiou, Maria; Pashalidis, Ioannis

    2013-02-01

    The uranium concentration and the isotopic ratio (238)U/(234)U have been determined in Cypriot groundwater samples by ICP-MS after ultrafiltration and acidification of the samples and α-spectroscopy after pre-concentration and separation of uranium by cation-exchange (Chelex 100 resin) and electro-deposition on stainless steel discs. The uranium concentration in the groundwater samples varies strongly between 0.1 and 40 μg l(-1). The highest uranium concentrations are found in groundwater samples associated with sedimentary rock formations and the obtained isotopic ratio (238)U/(234)U varies between 0.95 and 1.2 indicating basically the presence of natural uranium in the studied samples. The pH of the groundwater samples is neutral to weak alkaline (7 < pH < 8) and this is attributed to the carbonaceous content of the sedimentary rocks and the ophiolitic origin of the igneous rocks, which form the background geology in Cyprus. Generally, in groundwaters uranium concentration in solution increases with decreasing pH (7 < pH < 8) and this is attributed to the fact that at lower pH dissolution of soil minerals occurs, and uranium, which is adsorbed or forms solid solution with the geological matrix enters the aqueous phase. This is also corroborated by the strong correlation between the uranium concentration and the electrical conductivity (e.g. dissolved solids) measured in the groundwaters under investigation. PMID:23195433

  4. Determination of Toxic Metals in Little Cigar Tobacco with 'Triple Quad' ICP-MS.

    PubMed

    Pappas, R Steven; Martone, Naudia; Gonzalez-Jimenez, Nathalie; Fresquez, Mark R; Watson, Clifford H

    2015-06-01

    Smoking remains the leading cause of preventable death in the USA. Much of the focus on harmful and potentially harmful constituents (HPHCs) in tobacco products has been on cigarettes. Little cigars gained popularity over the last decade until tobacco taxes made cigarettes more expensive in the USA. Many little cigar brands are similar in size with cigarettes and may be smoked in a similar manner. Scant data are available on HPHC concentrations in little cigars, therefore we developed and applied a new analytical method to determine concentrations of 10 toxic metals in little cigar tobacco. The method utilizes 'triple quadrupole' ICP-MS. By optimizing octapole bias, energy discrimination and cell gas flow settings, we were able to accurately quantify a range of elements including those for which the cell gas reactions were endothermic. All standard modes (Single Quad No Gas, MS-MS NH3/He and MS-MS O2) were utilized for the quantitation of 10 toxic metals in little cigar tobacco, including uranium, which was added as an analyte in the new method. Because of the elimination of interfering ions at 'shifted analyte masses', detection limits were lower compared with a previous method. Tobacco selenium concentrations were below the limit of detection in the previous method, but the new technology made it possible to report all selenium concentrations.

  5. [Application of ICP-MS to Identify the Botanic Source of Characteristic Honey in South Yunnan].

    PubMed

    Wei, Yue; Chen, Fang; Wang, Yong; Chen, Lan-zhen; Zhang, Xue-wen; Wang, Yan-hui; Wu, Li-ming; Zhou, Qun

    2016-01-01

    By adopting inductively coupled plasma mass spectrometry (ICP-MS) combined with chemometric analysis technology, 23 kinds of minerals in four kinds of characteristic honey derived from Yunnan province were analyzed. The result showed that 21 kinds of mineral elements, namely Na, Mg, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Mo, Cd, Sb, Ba, Tl and Pb, have significant differences among different varieties of honey. The results of principal component analysis (PCA) showed that the cumulative variance contribution rate of the first four main components reached 77.74%, seven kinds of elements (Mg, Ca, Mn, Co, Sr, Cd, Ba) from the first main component contained most of the honey information. Through the stepwise discriminant analysis, seven kinds of elements (Mg, K, Ca, Cr, Mn, Sr, Pb) were filtered. out and used to establish the discriminant function model, and the correct classification rates of the proposed model reached 90% and 86.7%, respectively, which showed elements contents could be effectively indicators to discriminate the four kinds characteristic honey in southern Yunnan Province. In view of all the honey samples were harvested from apiaries located at south Yunnan Province where have similar climate, soil and other environment conditions, the differences of the mineral elements contents for the honey samples mainly due to their corresponding nectariferous plant. Therefore, it is feasible to identify honey botanical source through the differences of mineral elements.

  6. Determination of Toxic Metals in Little Cigar Tobacco with “Triple Quad” ICP-MS

    PubMed Central

    Pappas, R. Steven; Martone, Naudia; Gonzalez-Jimenez, Nathalie; Fresquez, Mark R.; Watson, Clifford H.

    2015-01-01

    Smoking remains the leading cause of preventable death in the United States. Much of the focus on harmful constituents (HPHCs) in tobacco products has been on cigarettes. Little cigars have gained popularity over the last decade as tobacco taxes made cigarettes more expensive in the U.S. Many little cigar brands are similar in size with cigarettes and may be smoked in a similar manner. Scant data are available on HPHC levels in little cigars, therefore we developed and applied a new analytical method to determine concentrations of ten toxic metals in little cigar tobacco. The method utilizes “triple quadrupole” ICP-MS. By optimizing octapole bias, energy discrimination, and cell gas flow settings, we were able to accurately quantify a range of elements including those for which the cell gas reactions were endothermic. All standard modes (Single Quad No Gas, MS/MS NH3/He, and MS/MS O2) were utilized for the quantitation of ten toxic metals in little cigar tobacco, including uranium, which was added as an analyte in the new method. Because of the elimination of interfering ions at “shifted analyte masses,” detection limits were lower compared to a previous method. Tobacco selenium concentrations were below the limit of detection in the previous method, but the new technology made it possible to report all selenium concentrations. PMID:25724197

  7. UV and IR laser ablation for inductively coupled plasma mass spectrometry

    SciTech Connect

    Smith, M.R.; Koppenaal, D.W.; Farmer, O.T.

    1993-06-01

    Laser ablation particle plume compositions are characterized using inductively coupled plasma mass spectrometry (ICP/MS). This study evaluates the mass response characteristics peculiar to ICP/MS detection as a function of laser fluence and frequency. Evaluation of the ICP/MS mass response allows deductions to be made concerning how representative the laser ablation produced particle plume composition is relative to the targeted sample. Using a black glass standard, elemental fractionation was observed, primarily for alkalis and other volatile elements. The extent of elemental fractionation between the target sample and the sampled plume varied significantly as a function of laser fluences and IR and UV laser frequency.

  8. Zircon U-Pb geochronological, geochemical, and Sr-Nd isotope data for Early Cretaceous mafic dykes in the Tancheng-Lujiang Fault area of the Shandong Province, China: Constraints on the timing of magmatism and magma genesis

    NASA Astrophysics Data System (ADS)

    Liu, Shen; Feng, Caixia; Hu, Ruizhong; Zhai, Mingguo; Gao, Shan; Lai, Shaocong; Yan, Jun; Coulson, Ian M.; Zou, Haibo

    2015-02-01

    The timing and source of magmatism that formed Early Cretaceous dolerite dykes in the Tancheng-Lujiang (Tan-Lu) Fault area of the southeastern North China Craton was determined using geochronological, geochemical, and whole-rock Sr-Nd isotopic data. Laser ablation-inductively coupled plasma-mass (LA-ICP-MS) spectrometry U-Pb analysis of zircon yielded consistent ages of 129.6 ± 0.7, 126.8 ± 0.7, 125.5 ± 0.7, 124.9 ± 0.9, 126.4 ± 0.7, and 125.5 ± 0.7 Ma for six samples of the mafic dykes within the NCC. The K2O + Na2O concentrations (5.02-5.21 wt.%) of the dykes indicate they are alkaline and these dykes have K2O concentrations (2.35-2.48 wt.%) that indicate they are shoshonitic. These dolerites are also characterized by high and wide ranging (La/Yb)N (14.5-36.0), have slightly negative Eu anomalies (δEu = 0.70-0.91) and positive Ba, U, K, and Pb anomalies, and are depleted in the high field strength elements (Nb, Ta, P, and Ti). In addition, these mafic dykes are characterized by high radiogenic Sr [(87Sr/86Sr)i = 0.7099-0.7100] and negative εNd (t) values (-14.4 to -13.7). These data suggest that the magmas that formed the dykes were derived through the partial melting (12.0-15.0%) of an enriched region of the mantle that was hybridized during interaction with subducted sedimentary rocks from the Yangtze Craton. The parental magmas then fractionated olivine and Fe-Ti oxides during ascent and underwent negligible crustal contamination during magma emplacement. These mafic magmas were finally emplaced as dyke swarms associated with lithospheric extension.

  9. Apatite U-Pb thermochronolgy applied to complex geological settings - insights from geo/thermochronology and geochemistry

    NASA Astrophysics Data System (ADS)

    Paul, Andre; Spikings, Richard; Ulyanov, Alexey; Chew, David

    2016-04-01

    Application of high temperature (>350oC) thermochronology is limited to the U-Pb system of accessory minerals, such as apatite, under the assumption that radiogenic lead is lost to thermally activated volume diffusion into an infinite reservoir. Cochrane et al. (2015) have demonstrated a working example from the northern Andes of South America. Predictions from volume diffusion theory were compared with measured single grain U-Pb date correlated to shortest diffusion radius and in-situ profiles measured by LA-ICP-MS. Results from both techniques were found to be in agreement with predictions from thermally activated, volume diffusion. However, outliers from the ID-TIMS data suggested some complexity, as grains were found to be too young relative to their diffusion radius. Interaction of multiple processes can be responsible for the alteration of apatite U-Pb dates such as: (1) metamorphic (over)growth, (2) fluid aided alteration/recrystallization and (3) metamictization and fracturing of the grain. Further, predictions from volume diffusion rely on the input parameters: (a) diffusivity, (b) activation energy and (c) shortest diffusion radius. Diffusivity and activation energy are potentially influenced by the chemical composition and subsequent changes in crystal structure. Currently there is one value for diffusion parameter and activation energy established for (Durango) apatite (Cherniak et al., 1991). Correlation between diffusivity/activation energy and composition has not been established. We investigate if correlations exist between diffusivity/activation energy and composition by obtaining single grain apatite U-Pb date and chemical compostion and correlating these to their diffusion radius. We test the consistency of apatite closure temperature, by comparing the apatite U-Pb dates with lower temperature thermochronometers such as white mica and K-feldspar Ar/Ar and by petrographic observations. We test if chemical information can be a proxy to identify

  10. Metallomics for drug development: an integrated CE-ICP-MS and ICP-MS approach reveals the speciation changes for an investigational ruthenium(III) drug bound to holo-transferrin in simulated cancer cytosol.

    PubMed

    Aleksenko, Svetlana S; Matczuk, Magdalena; Lu, Xifeng; Foteeva, Lidia S; Pawlak, Katarzyna; Timerbaev, Andrei R; Jarosz, Maciej

    2013-08-01

    A method based on combining inductively coupled plasma mass spectrometry (ICP-MS) with capillary electrophoresis (CE) or an ultrafiltration step was developed to study the speciation of the serum-protein adducts of a ruthenium anticancer drug under in vitro intracellular conditions. The formation of a reactive Ru species in the cell, following the metal release from the protein, is thought to play an important role in the drug's mode of action. Glutathione and ascorbic acid at their cancer cytosol concentrations were shown to be capable of altering the metal speciation in the drug adduct with holo-transferrin but not that with albumin. The appearance of the additional peaks in ICP-MS electropherograms (by recording both Ru- and Fe-specific signals) was found to be dependent on time which allowed for kinetic assessment of the evolution of novel metal species. On the contrary, after the addition of citric acid the ruthenium ion (within the appropriately complexed scaffold) remained sequestered in the adduct. This was inferred as a proof of the speciation changes taking place by a virtue of a redox mechanism rather than due to ligand-exchange transformations. The protein-bound metallodrug was further characterized by direct ICP-MS assaying so as to confirm a partial release of ruthenium induced by glutathione.

  11. Validation of Gold and Silver Nanoparticle Analysis in Fruit Juices by Single-Particle ICP-MS without Sample Pretreatment.

    PubMed

    Witzler, Markus; Küllmer, Fabian; Hirtz, Annika; Günther, Klaus

    2016-05-25

    With the increasing use of nanoparticles in consumer products, the need for validated quantitation methods also rises. This becomes even more urgent because the risks of nanomaterials are still not conclusively assessed. Fast, accurate, and robust single-particle (sp) ICP-MS is a promising technique as it is capable of counting and sizing particles at very low concentrations at the same time. Another feature is the simultaneous distinction between dissolved and particulate analytes. The present study shows, for the first time to our knowledge, a method validation for the rapid analysis of silver and gold nanoparticles with sp-ICP-MS in fruit juices without sample preparation. The investigated matrices water, orange juice, and apple juice were spiked with particles and only diluted prior to measurement without using a digestion reagent. The validations regarding particle size are successful according to the German GTFCh's guideline with deviations of accuracy and precision below 15%.

  12. Development and Validation of Simultaneous Analysis of Minerals and Toxic Elements in Foods by ICP-MS.

    PubMed

    Yutani, Aiko; Kishi, Eri; Ozaki, Asako; Shinya, Masanao; Ooshima, Tomoko; Yamano, Tetsuo

    2016-01-01

    We have developed and validated an inductively coupled plasma-mass spectrometry (ICP-MS) method for the simultaneous analysis of minerals and toxic elements in foods. Food samples were digested by microwave irradiation to prepare solutions for measurement by ICP-MS. Optimal gas mode and internal standard for each element were selected as appropriate. The method was validated for eighteen elements in total using three certified standard reference materials, namely, Typical Japanese Diet, Rice Flour-Unpolished and Infant/Adult Nutritional Formula, according to the guidelines of the Ministry of Health, Labour and Welfare of Japan. The trueness and precision of the method were all within the acceptable limits, except for Na in Rice Flour-Unpolished. PMID:27211920

  13. Method validation for determination of heavy metals in wine and slightly alcoholic beverages by ICP-MS

    NASA Astrophysics Data System (ADS)

    Voica, Cezara; Dehelean, Adriana; Pamula, A.

    2009-08-01

    The Organisation International de la Vigne et du Vin (OIV) fixed an uppermost level for some heavy metals in wine. Consequently, the need to determine very low concentration of elements that may be present in wine in trace and ultra trace levels occurred. Inductively coupled plasma mass spectrometry ICP-MS is considered an excellent tool for detailed characterization of the elementary composition of many samples, including samples of drinks. In this study a method of quantitative analysis for the determination of toxic metals (Cr, As, Cd, Ni, Hg, Pb) in wines and slightly alcoholic beverages by ICP-MS was validated. Several parameters have been taken into account and evaluated for the validation of method, namely: linearity, the minimum detection limit, the limit of quantification, accuracy and uncertainty.

  14. Triple Quad-ICP-MS Measurement of Toxic Metals in Mainstream Cigarette Smoke from Spectrum Research Cigarettes.

    PubMed

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

    2016-01-01

    We previously reported toxic metal concentrations in the mainstream smoke from 50 varieties of commercial cigarettes available in the USA using quadrupole inductively coupled plasma-mass spectrometry (ICP-MS). However, efforts to continue producing high quality data on select mainstream cigarette smoke constituents demand continued improvements in instrumentation and methodology and application of the methodology to cigarettes that differ in design or construction. Here we report a new application of 'triple quad'-ICP-MS instrumentation to analyze seven toxic metals in mainstream cigarette smoke from the Spectrum variable nicotine research cigarettes. The Spectrum cigarettes are available for research purposes in different configurations of low or conventional levels of nicotine, mentholated or nonmentholated, and tar delivery ranges described as 'low tar' or 'high tar'. Detailed characterizations of specific harmful or potentially harmful constituents delivered by these research cigarettes will help inform researchers using these cigarettes in exposure studies, cessation studies and studies related to nicotine addiction or compensation.

  15. Development of analytical techniques for ultra trace amounts of nuclear materials in environmental samples using ICP-MS for safeguards

    PubMed

    Magara; Hanzawa; Esaka; Miyamoto; Yasuda; Watanabe; Usuda; Nishimura; Adachi

    2000-07-01

    The authors have begun to develop analytical techniques for ultra trace amounts of nuclear materials and to prepare a clean chemistry laboratory for environmental sample analyses. The analytical techniques include bulk and particle analyses. For the bulk analysis, concentrations and isotopic ratios of U and/or Pu are determined by inductively-coupled plasma mass spectrometry (ICP-MS) and thermal ionization mass spectrometry (TIMS). In the particle analysis, isotopic ratios of U and/or Pu in each particle will be measured by secondary ion mass spectrometry (SIMS). This paper reports on the outline for the development of analytical techniques and the current situation of the development of the bulk analysis using ICP-MS is described.

  16. Routine analysis of ultra pure water by ICP-MS in the low- and sub-ng/L level.

    PubMed

    Hoelzl, R; Fabry, L; Kotz, L; Pahlke, S

    2000-01-01

    The chemical analysis with inductively coupled plasma-mass spectrometry (ICP-MS) can help to examine the purity of ultra pure water (UPW) down to 10 part per trillion (ng/L) and lower. For a proper determination of a high number of samples per week the analysis must be divided into two parts: the routine analysis and the reference water analysis. The routine analysis is done by direct measurement of the ultra pure water samples. Applying a standard addition method under particular clean conditions, the reference water analysis leads to the definition of the accurate zero. A quick evaluation scheme is also presented for the reference water analysis. The method is tested for its fitness for application by examining LOD (for relevant element < 2 ng/L), reproducibility and linearity of calibration. The ICP-MS was optimized according to the methodology of G. Taguchi to improve reproducibility and LOD. PMID:11225818

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

    SciTech Connect

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

    2013-06-01

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

  18. Sorption of Eu(III) on granite: EPMA, LA-ICP-MS, batch and modeling studies.

    PubMed

    Fukushi, Keisuke; Hasegawa, Yusuke; Maeda, Koushi; Aoi, Yusuke; Tamura, Akihiro; Arai, Shoji; Yamamoto, Yuhei; Aosai, Daisuke; Mizuno, Takashi

    2013-11-19

    Eu(III) sorption on granite was assessed using combined microscopic and macroscopic approaches in neutral to acidic conditions where the mobility of Eu(III) is generally considered to be high. Polished thin sections of the granite were reacted with solutions containing 10 μM of Eu(III) and were analyzed using EPMA and LA-ICP-MS. On most of the biotite grains, Eu enrichment up to 6 wt % was observed. The Eu-enriched parts of biotite commonly lose K, which is the interlayer cation of biotite, indicating that the sorption mode of Eu(III) by the biotite is cation exchange in the interlayer. The distributions of Eu appeared along the original cracks of the biotite. Those occurrences indicate that the prior water-rock interaction along the cracks engendered modification of biotite to possess affinity to the Eu(III). Batch Eu(III) sorption experiments on granite and biotite powders were conducted as functions of pH, Eu(III) loading, and ionic strength. The macroscopic sorption behavior of biotite was consistent with that of granite. At pH > 4, there was little pH dependence but strong ionic strength dependence of Eu(III) sorption. At pH < 4, the sorption of Eu(III) abruptly decreased with decreased pH. The sorption behavior at pH > 4 was reproducible reasonably by the modeling considering single-site cation exchange reactions. The decrease of Eu(III) sorption at pH < 4 was explained by the occupation of exchangeable sites by dissolved cationic species such as Al and Fe from granite and biotite in low-pH conditions. Granites are complex mineral assemblages. However, the combined microscopic and macroscopic approaches revealed that elementary reactions by a single mineral phase can be representative of the bulk sorption reaction in complex mineral assemblages. PMID:24171426

  19. Precise Measurement of Stable Neodymium Isotopes of Geological Materials by Using MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Ma, J.; Wei, G.; Liu, Y.; Ren, Z.; Xu, Y.

    2013-12-01

    A method has developed to determine high-precision high precision stable Nd isotopes in geological materials by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) using sample-standard-bracketing (SSB) mode. Nd was pre-concentrated and purifed and through a two column ion-exchange chromatographic procedure, yeilding a recovery of >96% for Nd with the interferences such as Ce and Sm being removed to cause little influence on the stable Nd isotopic compositions. The internal precision for the stable Nd isotopic compositions, ɛ142Nd, ɛ145Nd, ɛ146Nd and ɛ148Nd were generally better than ×0.2 (2SEM: standard error of the mean), and the external precision were generally better than ×0.2 (1SD: standard deviation) for ɛ142Nd, ɛ145Nd and ɛ146Nd, and better than ×0.5 (1SD) for ɛ148Nd estimated by the long-term results of the Nd standard solutions, such as La Jolla, Nd-GIG and NIST 3135a. Such precision id comparable to those by double spike method. Our measured ɛ142Nd, ɛ145Nd, ɛ146Nd and ɛ148Nd results of La Jolla are indentical to those by double spike method winthin analytical error. Thus, our method can provide comparable results for stable Nd isotopes to those by double spike method, but free from the inconvenience of calibrationg double spikes. This provides a more convenient means for studying stabe Nd isotopes in geological processes. By using this method, the stable Nd isotopic compositions for a series of international rock standard references were measured.

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

    SciTech Connect

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

    2009-05-21

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

  1. Measurement of arsenic and gallium content of gallium arsenide semiconductor waste streams by ICP-MS.

    PubMed

    Torrance, Keith W; Keenan, Helen E; Hursthouse, Andrew S; Stirling, David

    2010-01-01

    The chemistry of semiconductor wafer processing liquid waste, contaminated by heavy metals, was investigated to determine arsenic content. Arsenic and gallium concentrations were determined for waste slurries collected from gallium arsenide (GaAs) wafer processing at three industrial sources and compared to slurries prepared under laboratory conditions. The arsenic and gallium content of waste slurries was analyzed using inductively coupled plasma mass-spectrometry (ICP-MS) and it is reported that the arsenic content of the waste streams was related to the wafer thinning process, with slurries from wafer polishing having the highest dissolved arsenic content at over 1,900 mgL(-1). Lapping slurries had much lower dissolved arsenic (< 90 mgL(-1)) content, but higher particulate contents. It is demonstrated that significant percentage of GaAs becomes soluble during wafer lapping. Grinding slurries had the lowest dissolved arsenic content at 15 mgL(-1). All three waste streams are classified as hazardous waste, based on their solids content and dissolved arsenic levels and treatment is required before discharge or disposal. It is calculated that as much as 93% of material is discarded through the entire GaAs device manufacturing process, with limited recycling. Although gallium can be economically recovered from waste slurries, there is little incentive to recover arsenic, which is mostly landfilled. Options for treating GaAs processing waste streams are reviewed and some recommendations made for handling the waste. Therefore, although the quantities of hazardous waste generated are miniscule in comparison to other industries, sustainable manufacturing practices are needed to minimize the environmental impact of GaAs semiconductor device fabrication.

  2. Monthly-resolved coral skeletal lead isotopic determination in picogram quantities by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Chou, Y.; Shen, C.; Lo, Y.; Chang, C.

    2011-12-01

    Pb concentrations and isotopic composition in coral skeletons have been applied to understanding annual-decadal trends of natural hydrological evolution, ocean circulation, and anthropogenic pollution. However, the low Pb contents of only 10s-100s ng/g has hindered measurements of monthly-resolved coral Pb isotopic records and limited its applications. We refined chemistry and improved instrumental methodology to develop a reliable procedure for picogram-quantity coral Pb isotopic determination (Pb-204, Pb-206, Pb-207, and Pb-208) on a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS, Thermo Electron NEPTUNE). The overall procedural blank is <20 pg. Replicate measurements made on standard NIST SRM 981 shows that our method can achieve a precision of ± 300 ppm (2σ) for Pb-207/Pb-206 and Pb-208/Pb-206 with 100s-1000s pg of Pb. Monthly-resolution Pb isotopic and concentration records of a coral Porites collected by Son Tra Island, central Vietnam (16°12'59.4", 108°1'57.1") from 1978-2004 AD have been measured. Three features are exhibited as follows: (1) The high Pb/Ca background level of 0.652 μmol/mol after 1992, 1.5 times larger than value of 0.437 μmol/mol in 1978-1992, shows an impact of economic development on hydrological change. (2) Ratios of Pb-208/Pb-207, Pb-206/Pb-207, and Pb-206/Pb-204 are relatively low in winter and high in summer, reflecting different seasonal sources. (3) Significant Pb isotopic anomalies in 1991-1992 could result from the eruption of Mt. Pinatubo on June 15, 1991. Our results indicate that monthly-resolved coral Pb isotopic and concentration can be used as proxies of seasonal climate changes, volcanic impacts and humanity activities.

  3. Sorption of Eu(III) on granite: EPMA, LA-ICP-MS, batch and modeling studies.

    PubMed

    Fukushi, Keisuke; Hasegawa, Yusuke; Maeda, Koushi; Aoi, Yusuke; Tamura, Akihiro; Arai, Shoji; Yamamoto, Yuhei; Aosai, Daisuke; Mizuno, Takashi

    2013-11-19

    Eu(III) sorption on granite was assessed using combined microscopic and macroscopic approaches in neutral to acidic conditions where the mobility of Eu(III) is generally considered to be high. Polished thin sections of the granite were reacted with solutions containing 10 μM of Eu(III) and were analyzed using EPMA and LA-ICP-MS. On most of the biotite grains, Eu enrichment up to 6 wt % was observed. The Eu-enriched parts of biotite commonly lose K, which is the interlayer cation of biotite, indicating that the sorption mode of Eu(III) by the biotite is cation exchange in the interlayer. The distributions of Eu appeared along the original cracks of the biotite. Those occurrences indicate that the prior water-rock interaction along the cracks engendered modification of biotite to possess affinity to the Eu(III). Batch Eu(III) sorption experiments on granite and biotite powders were conducted as functions of pH, Eu(III) loading, and ionic strength. The macroscopic sorption behavior of biotite was consistent with that of granite. At pH > 4, there was little pH dependence but strong ionic strength dependence of Eu(III) sorption. At pH < 4, the sorption of Eu(III) abruptly decreased with decreased pH. The sorption behavior at pH > 4 was reproducible reasonably by the modeling considering single-site cation exchange reactions. The decrease of Eu(III) sorption at pH < 4 was explained by the occupation of exchangeable sites by dissolved cationic species such as Al and Fe from granite and biotite in low-pH conditions. Granites are complex mineral assemblages. However, the combined microscopic and macroscopic approaches revealed that elementary reactions by a single mineral phase can be representative of the bulk sorption reaction in complex mineral assemblages.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  5. [Determination of Trace Elements in Marine Cetaceans by ICP-MS and Health Risk Assessment].

    PubMed

    Ding, Yu-long; Ning, Xi; Gui, Duan; Mo, Hui; Li, Yu-sen; Wu, Yu-ping

    2015-09-01

    The liver, kidney and muscle samples from seven cetaceans were digested by microwave digestion, and trace elements amounts of V, Cd, Cu, Zn, As, Cr, Ni, Mn, Se, Hg and Pb were determined by inductively coupled plasma mass spectrometry (ICP-MS), and the health risk assessment for Zn, Cu, Cd, Hg, Se in the liver was conducted. The results of international lobster hepatopancreas standard (TORT-2) showed acceptable agreement with the certified values, and the relative standard deviation (RSD) of eleven kinds of trace elements were less than 3.54%, showing that the method is suitable for the determination of trace elements in cetaceans. The experimental results indicated that different tissues and organs of the dolphins had different trace elements, presenting the tissue specificity. There is a certain inter-species difference among different dolphins about the bioaccumulation ability of the trace elements. The distribution of trace elements in whales presented a certain regularity: the contents of most elements in liver, kidney were much higher than the contents of muscle tissues, Cu, Mn, Hg, Se, and Zn exhibit the higher concentrations in liver, while Cd was mainly accumulated in kidney. And according to the health risk assessment in liver, the exceeding standardrate of selenium and copper in seven kinds of whales was 100%, suggesting that these whales were suffering the contamination of trace elements. The experimental results is instructive to the study of trace elements in cetaceans, while this is the first report for the concentrations in organs of Striped dolphin, Bottlenose dolphin, Fraser's Dolphin and Risso's dolphin in China, it may provide us valuable data for the conservation of cetaceans.

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

    USGS Publications Warehouse

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

    2004-01-01

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

  7. [Determination of Trace Elements in Marine Cetaceans by ICP-MS and Health Risk Assessment].

    PubMed

    Ding, Yu-long; Ning, Xi; Gui, Duan; Mo, Hui; Li, Yu-sen; Wu, Yu-ping

    2015-09-01

    The liver, kidney and muscle samples from seven cetaceans were digested by microwave digestion, and trace elements amounts of V, Cd, Cu, Zn, As, Cr, Ni, Mn, Se, Hg and Pb were determined by inductively coupled plasma mass spectrometry (ICP-MS), and the health risk assessment for Zn, Cu, Cd, Hg, Se in the liver was conducted. The results of international lobster hepatopancreas standard (TORT-2) showed acceptable agreement with the certified values, and the relative standard deviation (RSD) of eleven kinds of trace elements were less than 3.54%, showing that the method is suitable for the determination of trace elements in cetaceans. The experimental results indicated that different tissues and organs of the dolphins had different trace elements, presenting the tissue specificity. There is a certain inter-species difference among different dolphins about the bioaccumulation ability of the trace elements. The distribution of trace elements in whales presented a certain regularity: the contents of most elements in liver, kidney were much higher than the contents of muscle tissues, Cu, Mn, Hg, Se, and Zn exhibit the higher concentrations in liver, while Cd was mainly accumulated in kidney. And according to the health risk assessment in liver, the exceeding standardrate of selenium and copper in seven kinds of whales was 100%, suggesting that these whales were suffering the contamination of trace elements. The experimental results is instructive to the study of trace elements in cetaceans, while this is the first report for the concentrations in organs of Striped dolphin, Bottlenose dolphin, Fraser's Dolphin and Risso's dolphin in China, it may provide us valuable data for the conservation of cetaceans. PMID:26669139

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

    PubMed Central

    2010-01-01

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

  9. The Alapaevsk-Sukhoi Log porphyry copper zone, Middle Urals: The U-Pb age of productive magmatism

    NASA Astrophysics Data System (ADS)

    Grabezhev, A. I.; Ronkin, Yu. L.; Puchkov, V. N.; Korovko, A. V.; Gerdes, A.; Azovskova, O. B.; Pribavkin, S. V.

    2014-12-01

    The Alapaevsk-Sukhoi Log zone about 100 km long and 3-10 km wide with numerous porphyry copper occurrences and small deposits is located in the eastern part of the East Ural volcanic megazone, Middle Urals. The long evolution of productive magmatism (according to the U-Pb (SHRIMP-II and LA-ICP-MS age of zircon) and its rejuvenation are established from the north and the south (Ma): from 411 ± 3 (Yalunina Gora pluton, town of Alapaevsk) to 404-406 ± 3 (Altynai-Artemovsk pluton, town of Artemovsk) and to 397 ± 4 (porphyric rhyodacites of the Shata area, town of Sukhoi Log). The K2O content in productive quartz diorites is 0.4-0.7, 0.8-1.2, and 0.4-0.7 wt %, respectively. The Mo-Cu porphyry occurrences are abundant in the Altynai-Artemovsk area. The granitic rocks of the quartz dioritic East Artemovsk pluton, which was recently found, are sericitized and contain significant sulfide mineralization. The structural position, age (365 ± 39 Ma, Rb-Sr errochron), composition of granitic rocks, and its mineralization are similar to those of the large (1.7 Mt Cu) Mikheevka deposit (U-Pb SHRIMP-II age of zircon is 356 ± 6 Ma) in the South Urals.

  10. Single particle ICP-MS characterization of titanium dioxide, silver, and gold nanoparticles during drinking water treatment.

    PubMed

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

    2016-02-01

    One of the most direct means for human exposure to nanoparticles (NPs) released into the environment is drinking water. Therefore, it is critical to understand the occurrence and fate of NPs in drinking water systems. The objectives of this study were to develop rapid and reliable analytical methods and apply them to investigate the fate and transportation of NPs during drinking water treatments. Rapid single particle ICP-MS (SP-ICP-MS) methods were developed to characterize and quantify titanium-containing, titanium dioxide, silver, and gold NP concentration, size, size distribution, and dissolved metal element concentration in surface water and treated drinking water. The effectiveness of conventional drinking water treatments (including lime softening, alum coagulation, filtration, and disinfection) to remove NPs from surface water was evaluated using six-gang stirrer jar test simulations. The selected NPs were nearly completely (97 ± 3%) removed after lime softening and alum coagulation/activated carbon adsorption treatments. Additionally, source and drinking waters from three large drinking water treatment facilities utilizing similar treatments with the simulation test were collected and analyzed by the SP-ICP-MS methods. Ti-containing particles and dissolved Ti were present in the river water samples, but Ag and Au were not present. Treatments used at each drinking water treatment facility effectively removed over 93% of the Ti-containing particles and dissolved Ti from the source water. PMID:26347937

  11. Single particle ICP-MS characterization of titanium dioxide, silver, and gold nanoparticles during drinking water treatment.

    PubMed

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

    2016-02-01

    One of the most direct means for human exposure to nanoparticles (NPs) released into the environment is drinking water. Therefore, it is critical to understand the occurrence and fate of NPs in drinking water systems. The objectives of this study were to develop rapid and reliable analytical methods and apply them to investigate the fate and transportation of NPs during drinking water treatments. Rapid single particle ICP-MS (SP-ICP-MS) methods were developed to characterize and quantify titanium-containing, titanium dioxide, silver, and gold NP concentration, size, size distribution, and dissolved metal element concentration in surface water and treated drinking water. The effectiveness of conventional drinking water treatments (including lime softening, alum coagulation, filtration, and disinfection) to remove NPs from surface water was evaluated using six-gang stirrer jar test simulations. The selected NPs were nearly completely (97 ± 3%) removed after lime softening and alum coagulation/activated carbon adsorption treatments. Additionally, source and drinking waters from three large drinking water treatment facilities utilizing similar treatments with the simulation test were collected and analyzed by the SP-ICP-MS methods. Ti-containing particles and dissolved Ti were present in the river water samples, but Ag and Au were not present. Treatments used at each drinking water treatment facility effectively removed over 93% of the Ti-containing particles and dissolved Ti from the source water.

  12. Kinetic energy discrimination in collision/reaction cell ICP-MS: Theoretical review of principles and limitations

    NASA Astrophysics Data System (ADS)

    Yamada, Noriyuki

    2015-08-01

    Kinetic energy discrimination (KED) is one of the means to control cell-formed interferences in collision/reaction cell ICP-MS, and also a technique to reduce polyatomic ion interferences derived from the plasma or vacuum interface in collision cell ICP-MS. The operation of KED is accurately described to explain how spectral interferences from polyatomic ions are reduced by this technique. The cell is operated under non-thermal conditions to implement KED, where the hard sphere collision model is aptly employed to portray the transmission of ions colliding with the cell gas that they don't chemically react with. It is theoretically explained that the analyte atomic ions surmount the energy barrier placed downstream of the cell and the interfering polyatomic ions do not due to their lower kinetic energy than the atomic ions, resulting in polyatomic interference reduction. The intrinsic limitations of this technique are shown to lie in the statistical nature of collision processes, which causes the broadening of ion kinetic energy distribution that hinders efficient KED. The reaction cell operation with KED, where plasma-derived interferences are reduced by the reactive cell gas while cell-formed interferences are suppressed by the energy barrier, is also described in a quantitative manner. This review paper provides an in-depth understanding of KED in cell-based ICP-MS for analysts to make better use of it.

  13. Do ICP-MS based methods fulfill the EU monitoring requirements for the determination of elements in our environment?

    PubMed

    Tirez, Kristof; Vanhoof, Chris; Bronders, Jan; Seuntjens, Piet; Bleux, Nico; Berghmans, Patrick; De Brucker, Nicole; Vanhaecke, Frank

    2015-12-01

    Undoubtedly, the most important advance in the environmental regulatory monitoring of elements of the last decade is the widespread introduction of ICP-mass spectrometry (ICP-MS) due to standards developed by the European Committee for Standardization. The versatility of ICP-MS units as a tool for the determination of major, minor and trace elements (Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, P, Pb, Sb, Se, Sn, Ti, V and Zn) in surface water, groundwater, river sediment, topsoil, subsoil, fine particulates and atmospheric deposition is illustrated in this paper. Ranges of background concentrations for major, minor and trace elements obtained from a regional case study (Flanders, Belgium) are summarized for all of these environmental compartments and discussed in the context of a harmonized implementation of European regulatory monitoring requirements. The results were derived from monitoring programs in support of EU environmental quality directives and were based on a selection of (non-polluted) background locations. Because of the availability of ICP-MS instruments nowadays, it can be argued that the main hindrance for meeting the European environmental monitoring requirements is no longer the technical feasibility of analysis at these concentration levels, but rather (i) potential contamination during sampling and analysis, (ii) too limited implementation of quality control programs, validating the routinely applied methods (including sampling and low level verification) and (iii) lack of harmonization in reporting of the chemical environmental status between the individual member states.

  14. Determination of 90Sr in contaminated environmental samples by tuneable bandpass dynamic reaction cell ICP-MS.

    PubMed

    Taylor, V F; Evans, R D; Cornett, R J

    2007-01-01

    A rapid method for the extraction and determination of 90Sr in natural water, plant and sediment samples was developed using extraction chromatography and dynamic reaction cell ICP-MS, with O2 as a reaction gas. While isobaric interference from the stable isotope 90Zr was efficiently removed by this method, interferences produced from in-cell reactions with Fe+ and Ni+ required suppression by tuneable bandpass, and in sediments, additional chromatographic separation. Method detection limits were 0.1 pg g-1 (0.5 Bq g-1), 0.04 pg g-1(0.2 Bq g-1), and 3 pg L-1 (5 Bq L-1) for sediments, plant and water samples, respectively, and 90Sr concentrations determined by ICP-MS were in good agreement with activities determined by Cerenkov counting and with certified reference values. While mass spectrometric determination does not rival detection limits achievable by radiometric counting, radiometric determination of 90Sr, a pure beta-emitter, is hindered by long analysis times (several weeks); the comparatively fast analysis achieved via ICP-MS enables same-day preparation and analysis of samples, making this an important technique for the environmental monitoring of areas contaminated by radioactivity. PMID:17111103

  15. Do ICP-MS based methods fulfill the EU monitoring requirements for the determination of elements in our environment?

    PubMed

    Tirez, Kristof; Vanhoof, Chris; Bronders, Jan; Seuntjens, Piet; Bleux, Nico; Berghmans, Patrick; De Brucker, Nicole; Vanhaecke, Frank

    2015-12-01

    Undoubtedly, the most important advance in the environmental regulatory monitoring of elements of the last decade is the widespread introduction of ICP-mass spectrometry (ICP-MS) due to standards developed by the European Committee for Standardization. The versatility of ICP-MS units as a tool for the determination of major, minor and trace elements (Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, P, Pb, Sb, Se, Sn, Ti, V and Zn) in surface water, groundwater, river sediment, topsoil, subsoil, fine particulates and atmospheric deposition is illustrated in this paper. Ranges of background concentrations for major, minor and trace elements obtained from a regional case study (Flanders, Belgium) are summarized for all of these environmental compartments and discussed in the context of a harmonized implementation of European regulatory monitoring requirements. The results were derived from monitoring programs in support of EU environmental quality directives and were based on a selection of (non-polluted) background locations. Because of the availability of ICP-MS instruments nowadays, it can be argued that the main hindrance for meeting the European environmental monitoring requirements is no longer the technical feasibility of analysis at these concentration levels, but rather (i) potential contamination during sampling and analysis, (ii) too limited implementation of quality control programs, validating the routinely applied methods (including sampling and low level verification) and (iii) lack of harmonization in reporting of the chemical environmental status between the individual member states. PMID:26487336

  16. [Research and Application of the ICP-MS Detection Technology for the Content of Nb and Ta in Geochemical Sample].

    PubMed

    Li, Zi-qiang; Li, Xiao-ying; Zhu, Kun; Xu, Xiao-xia; Yan, Zhi-yuan

    2015-08-01

    In order to provide the test analysis technology to support the exploration and development of niobium and tantalum resource, based on the special chemical properties of Nb and Ta in geochemical sample, we studied the detection methods for the content of Nb and Ta in geochemical sample by using inductively coupled plasma mass spectrometry (ICP-MS). The results show that the sample dissolution and instrumental parameter of ICP-MS, especially the former have significant influence? on detection results. Therefore, optimizing important parameters of sample dissolution is the key of the detection technology. The optimal parameters are that the weight of sample is 50 mg; the dosage of HF acid is 15 mL; the concentration of nitric acid and tartaric acid in the sample solution is 2% and 1.5%, respectively; the validity period of detection for sample solution ≤1 d. The detection method has been validated by the national geochemistry standard reference material. The precise and exaction of method meet the required of industry standards. The detection limits of method for Nb and Ta are 1.05 and 0.13 μg · g(-1), respectively. The experiment proved that the ICP-MS detection methods, which using certain preparation process of sample solutions, is suitable for accurate and rapid determination of Nb and Ta in geochemical sample, especially geochemical survey samples which with a large amount and low content of Nb and Ta. PMID:26672313

  17. Quantitative multi-element mapping of ancient glass using a simple and robust LA-ICP-MS rastering procedure in combination with image analysis.

    PubMed

    Selih, Vid S; van Elteren, Johannes T

    2011-08-01

    The surface of two glass artefacts in mosaic style, probably fragments of conglomerate glass bowls dating back two millennia, was investigated by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS). By rastering with the laser beam over a selected area of the surface of the glass artefacts, elemental oxide maps were generated. Quantification of the elemental oxides in the maps was achieved using a so-called sum normalization procedure, summating the elements-54 in total-as their oxides to 100% (w/w), without using an internal standard and applying only one external standard (NIST SRM glass 610). This results in a robust mapping procedure which automatically corrects for drift and defocusing issues. Sum normalization was applied to each pixel in the map separately and required a custom source code to process all the data in the tens of thousands of pixels to generate the elemental oxide concentration maps. The digital element maps generated upon rastering of the two glass artefacts are very compelling and are an excellent entry point to gain detailed insight into their fabrication and provenance using image analysis software for retrieval of localized elemental oxide concentrations and correlations.

  18. Investigating Compositional Variation of Ceramic Materials during the Late Neolithic on the Great Hungarian Plain - Preliminary LA-ICP-MS Results

    NASA Astrophysics Data System (ADS)

    Riebe, Danielle J.; Niziolek, Lisa C.

    2015-10-01

    Investigations have been undertaken to assess the extent to which compositional analysis can be used to determine trade and interaction on the Great Hungarian Plain during the Late Neolithic. Ceramic and clay samples in the Körös and Berettyó River Basins were analyzed at the Elemental Analysis Facilities (EAF) at The Field Museum of Natural History in Chicago, IL, USA. With the use of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), the aim of the project was to ascertain if micro-regional or site-specific compositional signatures could be determined in a region that is typically characterized as highly geologically homogenous. Identifying site-specific signatures enables archaeologists to model prehistoric interactions and, in turn, determine the relationship between interaction and various socio-cultural changes. This paper focuses on the preliminary compositional results of materials analyzed from three different sites across the Plain and the methodological implications for future anthropological research in the region.

  19. Rediscovering the palette of Alentejo (Southern Portugal) earth pigments: provenance establishment and characterization by LA-ICP-MS and spectra-colorimetric analysis

    NASA Astrophysics Data System (ADS)

    Gil, M.; Green, R.; Carvalho, M. L.; Seruya, A.; Queralt, I.; Candeias, A. E.; Mirão, J.

    2009-09-01

    Colored earth pigments sourced from Alentejo, Portugal, can be geologically categorized as either weathered carbonate rocks (terra rossas), schist units, or weathered iron ore deposits. The material was used until the mid-1900s by local residents as an ingredient in their traditional lime wash paintings and possibly in the production of artistic murals across the Alentejo region since pre-historic times. An integrated methodology incorporating laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and spectra-colorimetric analysis (CIELAB coordinates and reflectance curves), complemented by XRD, WDXRF, SEM-EDX, optical microscopy, and granulometric analysis, was used to characterize thirty-one Alentejo colored earths in an effort to correlate provenance with pigments properties. Data obtained from elemental analysis (major and trace) revealed a generic and similar elemental “fingerprint” that unable their distinction according to geographic provenance. Samples of weathered iron ore deposits derived from explored iron, copper, and sulfur mines are more easily discriminated using the chalcophilic (“sulfur-loving“) elements. Color analysis revealed a range of hues; olive-yellow to dark reddish-brown owing mainly to differences in the type and proportion of the color component present, independent of the accessory mineral.

  20. Absolute quantification of transferrin in blood samples of harbour seals using HPLC-ICP-MS.

    PubMed

    Grebe, Mechthild; Pröfrock, Daniel; Kakuschke, Antje; Broekaert, Jose A C; Prange, Andreas

    2011-02-01

    Harbour seals (Phoca vitulina) are bio-indicators for the assessment of their habitat and environmental changes. Besides population parameters and trends (survival, age structure, sex ratio), the individual health status represents a further important parameter for this assessment. The health status of seals is a complex and vague term, determined by a wide range of diagnostic parameters. Quantities of important blood proteins such as transferrin (Tf), as well as altered distribution patterns of its glycoforms, are frequently used as biomarkers in clinical diagnosis. Within this context Tf quantities and a varying pattern of its glycoforms are used as indicator for e.g. certain liver diseases, which also represents one of the most frequently observed pathological indication in harbour seals of the North Sea. Currently, most assay based quantification methods for Tf are limited since they often provide only information regarding the total Tf concentration rather than information of its different glycoforms. Due to a lack of suitable seal Tf antibodies also the application of more specific antibody based approaches is not possible. Within this background a new approach for the absolute quantification of the iron-transport protein Tf in the blood of harbour seals using its characteristic iron content and HPLC-ICP-MS detection is described. Method validation was performed using a certified human serum reference material (ERM-DA470K/IFCC). A Tf concentration of 2.33 ± 0.03 g L(-1) (sum of all quantified glycoforms) has been calculated, which is in good agreement with the certified total Tf concentration of 2.35 ± 0.08 g L(-1), confirming the accuracy of the proposed analytical method. Finally, different seal samples were analysed to demonstrate the suitability of the procedure for the quantification of Tf in real samples as well as to observe modified glycoform patterns. Compared to our previous studies for the first time it was possible to quantify the serum Tf

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

    PubMed

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

    2015-11-01

    In order to investigate the content and distribution of rare earth elements (REE) in main economic macroalgaes in our country, fifteen rare earth elements in three economic macroalgaes (including 30 samples of kelp, 30 samples of laver and 15 samples of Enteromorpha) were detected using ICP-MS method. Results showed that the total content of REE in different species of macroalgaes was different. The highest total content of REE was in Enteromorpha (16,012.0 ng · g⁻¹), while in kelp and laver, the total REE was similar for two macroalgaes (3887.4 and 4318.1 ng · g⁻¹ respectively). The content of fifteen rare earth elements in kelp ranged from 7.9 to 1496.4 ng · g⁻¹; in laver, it ranged from 8.2 to 1836.6 ng · g⁻¹. For Enteromorpha, the concentration of 15 rare earth elements were between 19.2 and 6014.5 ng · g⁻¹. In addition, the content and distribution of different rare earth elements in different macroalgaes was also different. For kelp, the highest content of REE was Ce (1 496.4 ng · g⁻¹), and the second was La (689.1 ng · g⁻¹). For laver, the highest was Y (1836.6 ng · g⁻¹), and the second was Ce (682.2 ng · g⁻¹). For Enteromorpha, the highest was Ce (6014.5 ng · g⁻¹), and the second was La (2902.9 ng · g⁻¹). Present results also showed that three macroalgaes accumulated the light rare earth elements much more than the high rare earth elements. The light rare earth elements occupied 90.9%, 87.3% and 91.1% for kelp, laver and Enteromorpha respectively. The result that the Enteromorpha had high content of rare earth elements could provide important support for opening new research directions for the utilization of Enteromorpha. PMID:26978935

  2. Danube catchment water chemistry monitoring - elemental pattern determination from source to mouth using ICP-MS

    NASA Astrophysics Data System (ADS)

    Tchaikovsky, Anastassiya; Zitek, Andreas; Irrgeher, Johanna; Prohaska, Thomas

    2014-05-01

    Monitoring the elemental composition of river water is an important tool to determine the chemical status of a river. However, currently many studies are limited to the analysis of heavy metals included in the EU Water Framework Directive Priority Substances List (Cd, Hg, Ni, Pb). Yet, the assessment of further elements (e.g. Ca, Mg, Si) can give additional relevant information for understanding catchment processes such as soil erosion, weathering, hydrological changes or glacial melting. In addition, site specific "elemental pattern" can be used as tracer for ecological studies, like habitat and migration studies of fish or birds. Elemental information is of particular interest complementary to isotopic data where only little variability in the isotopic signatures can be observed. In this work, we investigated water samples collected from 68 sampling sites along the longitudinal course of the river Danube including the major tributaries during the Joint Danube Survey 3 (JDS3) in 2013. Water samples were obtained as triplicates in the middle of the river and analyzed using Inductively Coupled - Plasma Mass Spectrometry (ICP-MS). Method validation was performed using riverine water (NRC SLRS-5) certified reference material as well as in-house prepared quality control standards. Due to the diverse geology and changing natural and anthropogenic factors along the longitudinal course of the Danube, pronounced elemental variations among the water samples were documented. For instance, especially some major elements (Ca, K, Mg, Na) together with some minor elements (Si, Sr) are known to reflect in particular regional geological morphologies. In addition, the variation in Si/Ca ratios can be used as an indicator for weathering conditions, especially in the mountainous areas along the Danube. Elevated concentrations of Cd, Cu, Fe, Ni, and Pb downstream of some large cities and industrial areas are signs of significant anthropogenic impact. In combination, the chemical

  3. Element-tracing of mineral matters in Dendrobium officinale using ICP-MS and multivariate analysis.

    PubMed

    Zhu, Nannan; Han, Shen; Yang, Chunning; Qu, Jixu; Sun, Zhirong; Liu, Wenjie; Zhang, Xiaomin

    2016-01-01

    Rare studies have been performed to trace the mineral elements in Dendrobium officinale. In this study, we aim to trace the mineral elements in D. officinale collected from ten geographical locations in China. ICP-MS system was used for simultaneous determination of mineral elements. Principal component analysis was performed using the obtained data in the quantification of mineral contents. Cluster analysis was performed using the Ward's method. Several of essential microelments were detected in D. officinale, including ferrum (Fe), manganese (Mn), zinc (Zn), chromium (Cr), nickel (Ni) and vanadium (V). Among these elements, three elements (i.e. Fe, Mn and Zn) were highly and simultaneously detected in the D. officinale collected from the ten locations. The level of Ni was positively associated with that of Zn (r = 0.986, P < 0.01). The level of titanium (Ti) was positively associated with that of V (r = 0.669, P < 0.05), and negatively associated with Cr (r = -0.710, P < 0.05). In addition, the level of Mn was positively associated with that of barium (r = 0.749, P < 0.05). Further, the level of Fe was positively associated with that of Ni (r = 0.664, P < 0.05), Zn (r = 0.742, P < 0.05), and rare earth elements (r = 0.847, P < 0.01), respectively. Three eigenvalues explained about 86.60 % of the total variance, which contributed significantly to the explanation of cumulative variance. Cluster analysis indicated the cultivars were categorized into 3 clusters. Ni, Zn, Fe, Cr, Ti and rare earth elements were designated as the characteristic elements. Cultivars collected from Yulin, Menghai, and Shaoguan ranked the top 3 in the comprehensive scores, indicating the content of the mineral elements was comparatively higher in these locations. PMID:27429889

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

    PubMed

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

    2015-11-01

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

  5. High precision Mg and Cr isotope measurements by MC-ICP-MS and their applications to date the first stage of planet formation in the early solar nebula.

    NASA Astrophysics Data System (ADS)

    Yin, Q.; Jacobsen, B.; Moynier, F.

    2008-05-01

    We developed high precision Mg and Cr isotope measurement techniques by MC-ICP-MS at UC Davis to probe physicochemical conditions in the early solar nebula and establish high-resolution chronology from dust to the earliest planet building processes. (1) We obtained stable isotopic composition of Mg (δ25Mg) together with δ26Mg*, the radiogenic in growth from the decay of the short-lived, now extinct 26Al (T1/2 ~0.7 Myr) in whole rock fragments and mineral separates from high temperature refractory Ca-Al-rich inclusions (CAIs) in primitive meteorite Allende, the oldest known (first) solid objects in our solar system. Enrichment of heavy Mg isotopes (up to +6 permil) in d25Mg suggest that the igneous Type B CAIs have lost 14-47 percent of original Mg by evaporation in the early solar nebular during high temperature. Compact and fluffy Type A CAIs, on the other hand, shows light isotope enrichment with d25Mg as low as -4 permil), suggesting condensation from a nebular gas already depleted in heavy Mg isotopes. All of these objects plot on a well-defined 26Al-26Mg isochron with 26Al/27Al=(5.17+/-0.10)x10-5, suggesting the total duration of CAI formation event is less than 20,000 years. U-Pb dating in the same material anchors the event at 4567.4+/-0.3 Myr ago [1]. (2) We have applied 53Mn-53Cr chronometer to date chondrule obtained from primitive chondrite, and establish that chondrules in ordinary chondrite postdate the CAI by ~2 Myr [2]. (3) We further apply 53Mn-53Cr chronometer to a suite of carbonaceous chondrites whole rock samples, which are "cosmic sediments" made of CAIs and chondrules that are "cemented" together by fine grained matrices rich in organics and presolar grains. All carbonaceous chondrites exhibit 53Cr* anomalies that are correlated with 55Mn/52Cr ratio, which in turn is governed by proportion of matrix/refractory components. Thus 53Mn-53Cr chronometer dates the accretion timescale ("sedimentation" or "compaction" time) of undifferentiated

  6. CA-TIMS zircon U-Pb dating of felsic ignimbrite from the Binchuan section: Implications for the termination age of Emeishan large igneous province

    NASA Astrophysics Data System (ADS)

    Zhong, Yu-Ting; He, Bin; Mundil, Roland; Xu, Yi-Gang

    2014-09-01

    The age of the Emeishan lavas in SW China remains poorly constrained because the extrusive rocks are (1) thermally overprinted and so represent an open system unsuitable for 40Ar/39Ar geochronology and (2) in most cases devoid of zircon so that it is impossible for the application of U-Pb geochronology. Existing radiometric age constraints of Emeishan large igneous province are mainly from the application of SIMS and LA-ICP-MS U-Pb techniques to zircons from mafic and felsic intrusions, which represent indirect constraints for the lavas. In an attempt to directly determine the age of the Emeishan lava succession, high-resolution chemical abrasion-thermal ionization mass spectrometry (CA-TIMS) zircon U-Pb techniques have been used on the felsic ignimbrite at the uppermost part of the Emeishan lava succession. These techniques have yielded a weighted mean 206Pb/238U age of 259.1 ± 0.5 Ma (n = 6; MSWD = 0.7). We interpret this age as the termination age of the Emeishan flood basalts. The age of the Guadalupian-Lopingian boundary is still unconstrained by high-resolution geochronology but is likely to be close to our new age for this felsic ignimbrite.

  7. Measurement of elemental speciation by liquid chromatography -- inductively coupled plasma mass spectrometry (LC-ICP-MS) with the direct injection nebulizer (DIN)

    SciTech Connect

    Shum, S.

    1993-05-01

    This thesis is divided into 4 parts: elemental speciation, speciation of mercury and lead compounds by microbore column LC-ICP-MS with direct injection nebulization, spatially resolved measurements of size and velocity distributions of aerosol droplets from a direct injection nebulizer, and elemental speciation by anion exchange and size exclusion chromatography with detection by ICP-MS with direct injection nebulization. Tabs, figs, refs.

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

    PubMed

    Schwarz, A; Heumann, K G

    2002-09-01

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

  9. Can we trust mass spectrometry for determination of arsenic peptides in plants: comparison of LC-ICP-MS and LC-ES-MS/ICP-MS with XANES/EXAFS in analysis of Thunbergia alata.

    PubMed

    Bluemlein, Katharina; Raab, Andrea; Meharg, Andrew A; Charnock, John M; Feldmann, Jörg

    2008-04-01

    The weakest step in the analytical procedure for speciation analysis is extraction from a biological material into an aqueous solution which undergoes HPLC separation and then simultaneous online detection by elemental and molecular mass spectrometry (ICP-MS/ES-MS). This paper describes a study to determine the speciation of arsenic and, in particular, the arsenite phytochelatin complexes in the root from an ornamental garden plant Thunbergia alata exposed to 1 mg As L(-1) as arsenate. The approach of formic acid extraction followed by HPLC-ES-MS/ICP-MS identified different As(III)-PC complexes in the extract of this plant and made their quantification via sulfur (m/z 32) and arsenic (m/z 75) possible. Although sulfur sensitivity could be significantly increased when xenon was used as collision gas in ICP-qMS, or when HR-ICP-MS was used in medium resolution, the As:S ratio gave misleading results in the identification of As(III)-PC complexes due to the relatively low resolution of the chromatography system in relation to the variety of As-peptides in plants. Hence only the parallel use of ES-MS/ICP-MS was able to prove the occurrence of such arsenite phytochelatin complexes. Between 55 and 64% of the arsenic was bound to the sulfur of peptides mainly as As(III)(PC(2))(2), As(III)(PC(3)) and As(III)(PC(4)). XANES (X-ray absorption near-edge spectroscopy) measurement, using the freshly exposed plant root directly, confirmed that most of the arsenic is trivalent and binds to S of peptides (53% As-S) while 38% occurred as arsenite and only 9% unchanged as arsenate. EXAFS data confirmed that As-S and As-O bonds occur in the plants. This study confirms, for the first time, that As-peptides can be extracted by formic acid and chromatographically separated on a reversed-phase column without significant decomposition or de-novo synthesis during the extraction step. PMID:18084749

  10. Can we trust mass spectrometry for determination of arsenic peptides in plants: comparison of LC-ICP-MS and LC-ES-MS/ICP-MS with XANES/EXAFS in analysis of Thunbergia alata.

    PubMed

    Bluemlein, Katharina; Raab, Andrea; Meharg, Andrew A; Charnock, John M; Feldmann, Jörg

    2008-04-01

    The weakest step in the analytical procedure for speciation analysis is extraction from a biological material into an aqueous solution which undergoes HPLC separation and then simultaneous online detection by elemental and molecular mass spectrometry (ICP-MS/ES-MS). This paper describes a study to determine the speciation of arsenic and, in particular, the arsenite phytochelatin complexes in the root from an ornamental garden plant Thunbergia alata exposed to 1 mg As L(-1) as arsenate. The approach of formic acid extraction followed by HPLC-ES-MS/ICP-MS identified different As(III)-PC complexes in the extract of this plant and made their quantification via sulfur (m/z 32) and arsenic (m/z 75) possible. Although sulfur sensitivity could be significantly increased when xenon was used as collision gas in ICP-qMS, or when HR-ICP-MS was used in medium resolution, the As:S ratio gave misleading results in the identification of As(III)-PC complexes due to the relatively low resolution of the chromatography system in relation to the variety of As-peptides in plants. Hence only the parallel use of ES-MS/ICP-MS was able to prove the occurrence of such arsenite phytochelatin complexes. Between 55 and 64% of the arsenic was bound to the sulfur of peptides mainly as As(III)(PC(2))(2), As(III)(PC(3)) and As(III)(PC(4)). XANES (X-ray absorption near-edge spectroscopy) measurement, using the freshly exposed plant root directly, confirmed that most of the arsenic is trivalent and binds to S of peptides (53% As-S) while 38% occurred as arsenite and only 9% unchanged as arsenate. EXAFS data confirmed that As-S and As-O bonds occur in the plants. This study confirms, for the first time, that As-peptides can be extracted by formic acid and chromatographically separated on a reversed-phase column without significant decomposition or de-novo synthesis during the extraction step.

  11. Ion microprobe U-Pb dating and strontium isotope analysis of biogenic apatite

    NASA Astrophysics Data System (ADS)

    Sano, Y.; Toyoshima, K.; Takahata, N.; Shirai, K.

    2012-12-01

    Conodonts are micro-fossils chemically composed of apatite which occurred in the body of one animal. They are guide fossils to show formation ages of sedimentary sequences with the highest resolution [1] and good samples to verify the dating method. We developed the ion microprobe U-Pb dating of apatite [2] and applied the method to a Carboniferous conodont [3] by using a SHRIMP II installed at Department of Earth and Planetary Sciences, Hiroshima University. Recently we have developed the NanoSIMS U-Pb dating method and successfully measured the formation ages of monazite [4] and zircon [5] at Atmosphere and Ocean Research Institute, University of Tokyo. In this work we carried out the NanoSIMS U-Pb dating of biogenic apatite such as conodont. Since the spot size of NanoSIMS is smaller than SHRIMP II, it is easier to have multi-spots on the single fragment of biogenic apatite. Based on the isochron method of U-Pb system, we have calculated the formation ages. They are consistent with those in literature. In order to study the chemical evolution of ocean during the past 600 Million years, strontium isotopes (87Sr/86Sr) of fossil marine carbonate such as coral skeletons and foraminifera tests were measured and compiled [6]. However they are not robust when the age is older than 500Ma, partly due to post-depositional histories. Apatite is more stable and more resistant to the alteration than carbonate [7]. Recently we have developed the method of NanoSIMS strontium isotopic analysis of a fish otolith, which composed of aragonite [8]. In this work we carried out the strontium isotopic analysis of biogenic apatite. The advantage of the ion microprobe technique over the TIMS (thermal ionization mass spectrometer) and MC-ICP-MS (multi-collector inductively coupled argon plasma mass spectrometer) method is preservation of the important textural context and to provide an opportunity for other simultaneous analytical work with high spatial resolution. This is the case for

  12. Trace element speciation in largemouth bass ( Micropterus salmoides) from a fly ash settling basin by liquid chromatography-ICP-MS.

    PubMed

    Jackson, B P; Shaw Allen, P L; Hopkins, W A; Bertsch, P M

    2002-09-01

    Analytical techniques used to examine the chemical speciation of multiple trace elements are important for the investigation of biological systems. Size exclusion chromatography (SEC) coupled to ICP-MS was used to investigate the speciation of Se, As, Cu, Cd and Zn in tissue extracts from a largemouth bass (Micropterus salmoides) collected from a coal fly ash basin and results were compared to a largemouth bass collected at a reference site. Using a Biosil SEC column, with an effective separation range of 100-7 KDa, Cu, Zn and Cd were shown to be bound to metallothionein (MT) in the liver, gill and, to a lesser extent, gonad tissue extract. In liver, muscle and gill of the ash basin bass, Se was predominantly present as low molecular weight species. Only in the gonad extract was the major fraction of Se associated with high molecular weight species. For the liver and gill extracts, further SEC-ICP-MS on a column with an effective separation range of 7000-500 Da was performed, but Se species still eluted near the total volume of the column suggesting a low molecular weight organic or inorganic species. Ion chromatography (IC)-ICP-MS using an AS7 column and HNO(3) gradient elution indicated that the Se and As species in the liver and gill extracts had similar retention times but these retention times did not correspond to retention times for As(III), As(V), dimethylarsenate, arsenobetaine, Se(IV), Se(VI), seleno-methionine, or seleno-cystine.

  13. Development of a mild mercaptoethanol extraction method for determination of mercury species in biological samples by HPLC-ICP-MS.

    PubMed

    Wang, Meng; Feng, Weiyue; Shi, Junwen; Zhang, Fang; Wang, Bing; Zhu, Motao; Li, Bai; Zhao, Yuliang; Chai, Zhifang

    2007-03-30

    A mild, efficient and convenient extraction method of using 2-mercaptoethanol contained extractant solution combined with an incubator shaker for determination of mercury species in biological samples by HPLC-ICP-MS has been developed. The effects of the concentration of 2-mercaptoethanol, the composition of the extractant solution and the shaking time on the efficiency of mercury extraction were evaluated. The optimization experiments indicated that the quantitative extraction of mercury species from biological samples could be achieved by using 0.1% (v/v) HCl, 0.1% (v/v) 2-mercapoethanol and 0.15% (m/v) KCl extractant solution in an incubator shaker for shaking overnight (about 12h) at room temperature. The established method was validated by analysis of various biological certified reference materials, including NRCC DOLT-3 (dogfish liver), IAEA 436 (tuna fish), IAEA MA-B-3/TM (garfish filet), IAEA MA-M-2/TM (mussel tissue), GBW 08193 (bovine liver) and GBW 08572 (prawn). The analytical results of the reference materials were in good agreement with the certified or reference values of both methyl and total mercury, indicating that no distinguishable transformation between mercury species had occurred during the extraction and determination procedures. The limit of detection (LOD) for methyl (CH(3)Hg(+)) and inorganic mercury (Hg(2+)) by the method are both as 0.2microg L(-1). The relative standard deviation (R.S.D.s) for CH(3)Hg(+) and Hg(2+) are 3.0% and 5.8%, respectively. The advantages of the developed extraction method are that (1) it is easy to operate in HPLC-ICP-MS for mercury species determination since the extracted solution can be directly injected into the HPLC column without pH adjustment and (2) the memory effect of mercury in the ICP-MS measurement system can be reduced.

  14. Focused microwave-induced combustion for digestion of botanical samples and metals determination by ICP OES and ICP-MS.

    PubMed

    Barin, J S; Pereira, J S F; Mello, P A; Knorr, C L; Moraes, D P; Mesko, M F; Nóbrega, J A; Korn, M G A; Flores, E M M

    2012-05-30

    The advantages and shortcomings of focused microwave-induced combustion (FMIC) for digestion of plant samples were studied. The effects of sample mass, absorbing solution, oxygen gas flow-rate, and time of reflux step on recoveries of major, minor and trace metals were systematically evaluated. Afterwards, Al, Ba, Ca, Co, Cr, Cu, Mg, Mn, Ni, Sr, V, and Zn were determined by inductively coupled plasma optical emission spectrometry (ICP OES) and by inductively coupled plasma mass spectrometry (ICP-MS). The main advantages of FMIC when compared to microwave-assisted wet digestion (MAWD) and focused-microwave-assisted wet digestion (FMAWD) are the possibility to digest larger masses of samples (up to 3g) using shorter heating times and diluted nitric acid solution for absorbing all analytes. Using the selected experimental conditions for FMIC, residual carbon content was lower than 0.7% for all samples and relative standard deviation (RSD) varied from 1.5 to 14.1%. Certified reference materials (NIST 1515 apple leaves and NIST 1547 peach leaves) were used for checking accuracy and determined values for all metals were in agreement with certified values at a 95% confidence level. No statistical difference (ANOVA, 95% of confidence level) was observed for results obtained by FMIC, FMAWD, and MAWD. Limits of detection were lower when using FMIC in the range of 0.02-0.15 μg g(-1) for ICP OES and 0.001-0.01 μg g(-1) for ICP-MS, which were about 3 and 6 times lower than the values obtained by FMAWD and MAWD, respectively. It is important to point out that FMIC was a suitable sample preparation method for major, minor and trace metals by both determination techniques (ICP OES and ICP-MS). Additionally, since it allows lower LODs (because up to 3g of sample can be digested) and diluted acid solutions are used (without any further dilution), the use of ICP-MS is not mandatory. PMID:22608453

  15. Selected isotope ratio measurements of light metallic elements (Li, Mg, Ca, and Cu) by multiple collector ICP-MS

    PubMed Central

    Platzner, Thomas I.; Segal, Irina

    2007-01-01

    The unique capabilities of multiple collector inductively coupled mass spectrometry (MC-ICP-MS) for high precision isotope ratio measurements in light elements as Li, Mg, Ca, and Cu are reviewed in this paper. These elements have been intensively studied at the Geological Survey of Israel (GSI) and other laboratories over the past few years, and the methods used to obtain high precision isotope analyses are discussed in detail. The scientific study of isotopic fractionation of these elements is significant for achieving a better understanding of geochemical and biochemical processes in nature and the environment. PMID:17962922

  16. Determination of naturally-occurring actinides and their progeny in fresh water using ICP-MS and batch separation

    SciTech Connect

    Crain, J.S.; Alvarado, J.A.; Kiely, J.T.

    1995-12-01

    The determination of naturally-occurring actinides (including progeny such as {sup 230}Th) in fresh water is of significance in limnology, hydrology, and environmental monitoring. In many instances, these determinations require multiple analyses and a combination of radiometric and elemental measurement techniques (e.g., alpha spectrometry and thermal ionization mass spectrometry). In this work, we will describe the use of a single technique, inductively coupled plasma-mass spectrometry (ICP-MS), for these determinations. We will also describe the batch separation chemistry used to facilitate these determinations in ground and surface water, where natural analyte concentrations run between 1 {mu}g/L and 1 {mu}g/L.

  17. Analysis of IAEA Environmental Samples for Plutonium and Uranium by ICP/MS in Support Of International Safeguards

    SciTech Connect

    Farmer, Orville T.; Olsen, Khris B.; Thomas, May-Lin P.; Garofoli, Stephanie J.

    2008-05-01

    A method for the separation and determination of total and isotopic uranium and plutonium by ICP-MS was developed for IAEA samples on cellulose-based media. Preparation of the IAEA samples involved a series of redox chemistries and separations using TRU® resin (Eichrom). The sample introduction system, an APEX nebulizer (Elemental Scientific, Inc), provided enhanced nebulization for a several-fold increase in sensitivity and reduction in background. Application of mass bias (ALPHA) correction factors greatly improved the precision of the data. By combining the enhancements of chemical separation, instrumentation and data processing, detection levels for uranium and plutonium approached high attogram levels.

  18. Determination of impurities in uranium matrices by time-of-flight ICP-MS using matrix-matched method

    SciTech Connect

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

    2007-01-01

    The analysis of impurities in uranium matrices is performed in a variety of fields, e.g. for quality control in the production stream converting uranium ores to fuels, as element signatures in nuclear forensics and safeguards, and for non-proliferation control. We have investigated the capabilities of time-of-flight ICP-MS for the analysis of impurities in uranium matrices using a matrix-matched method. The method was applied to the New Brunswick Laboratory CRM 124(1-7) series. For the seven certified reference materials, an overall precision and accuracy of approximately 5% and 14%, respectively, were obtained for 18 analyzed elements.

  19. U-Pb age and Hf isotope data of detrital zircons of exotic Devonian sandstones from the southeastern Rheinisches Schiefergebirge near Giessen, Germany

    NASA Astrophysics Data System (ADS)

    Nawrat, Joscha; Bahlburg, Heinrich; Axel, Gerdes

    2013-04-01

    In the Rhenohercynian zone, southeastern Rheinisches Schiefergebirge, of Germany early and late Devonian sedimentary successions of suspect provenance occur in the allochthonous assemblage of the Lindener Mark south of Giessen and the Giessen nappe. Both tectonic units were emplaced over the autothonous Rhenohercynian units as northward moving nappes during the Variscan orogeny. A combination of faunal and sedimentological data suggested that the allochthonous sedimentary successions do not belong to the Rhenohercynian zone as part of the southern margin of the Old Red Continent and most likely derive originally from northern Gondwana. In order to test the interpretation of a NW African origin of the Hercynian units we applied U-Pb detrital zircon age determination and Hf isotope analysis by laser-ablation-sector field-inductively coupled plasma mass spectrometry (LA-SF-ICP-MS). We studied the Dalmanitensandstein in the Lindener Mark south of Giessen, the Giessener Grauwacke, Kalkige Grauwacke and the Erbslochgrauwacke near Marburg and Densberg. We analyzed around 150 detrital zircons of each sample and considered only ages which are less than 10% discordant. Viewed synoptically the age distributions of all 5 samples are very similar. The U-Pb ages range between 3300 Ma and 372 Ma. The age distributions show two major peaks in each of the samples. The older peak is around 2000 Ma with ~27% of ages, the younger one is around 600 Ma with ~71% of ages. Ages between 1650 and 1200 Ma are very scarce (~2%). These essentially bimodal zircon age spectra are similar to typical NW African zircon age spectra with the main abundances connected to the Eburnean and Cadomian orogenies at c. 2000 Ma and c. 600 Ma, respectively. Contrastingly, siliciclastic units derived from the Old Red Continent to the north include abundant zircon ages between 2000 and 1000 Ma. The Hf isotope patterns of the samples of all studied formations are also very similar. The Hf isotopic compositions of

  20. U-Pb SHRIMP geochronology of leucogranites from the Greater Himalayan Sequence in Zanskar and from the Karakoram fault zone, NW India

    NASA Astrophysics Data System (ADS)

    Horton, F.; Sommerfeld, J.; Hassett, W. C.; Leech, M. L.

    2010-12-01

    New U-Pb SHRIMP ages have been obtained from the westernmost limb of the South Tibetan Detachment in northwest India, locally known as the Zanskar Shear Zone (ZSZ), and from the dextral strike-slip Karakoram fault zone. This research investigates the extent of mid-crustal anatexis and ductile exhumation of the Greater Himalaya Sequence (GHS) in the western Himalaya, and explores a possible relationship between Zanskar and Karakoram fault zone leucogranites. Zircon Hf isotope signatures, measured with laser ablation ICP-MS, identify potential sources of the anatectic leucogranites. Along the ZSZ, samples were collected from the Nun-Kun and Suru valleys in the west and from Haptal valley ~100 km to the southeast. Leucogranite from the lowest structurally-exposed GHS in Suru valley yields a monazite age of 19.2±0.4 Ma, which is significantly younger than the 25.1±0.6 Ma monazite age of a psammitic schist near the ZSZ. Monazites give an age of 20.7±0.4 Ma for a Haptal valley migmatite and an adjacent late-stage pegmatite dike in a small leucogranite pluton has monazite ages ranging from 25.9±1.3 to 19.0±0.9 Ma. While these ages suggest coeval leucogranite emplacement along the entire ZSZ, only leucogranites in the east yielded inherited monazite ages of ~470 Ma and ~450 Ma that are indicative of a Cambro-Ordovician pan-African source. The western segment of the ZSZ exhibits less extensional offset and leucocratic melts appear to have migrated further from migmatite source regions than in the east. These along-strike variations suggest that the structural transition from a compact shear zone in the east to dispersed extensional shear zones near Pensi La may represent the westernmost extent of ductile melt-facilitated GHS exhumation. Miocene leucogranite emplacement also occurred along the Karakoram fault, which raises the question of whether the fault served as a conduit for mid-crustal GHS melts. In Nubra Valley, a leucogranite from the Karakoram fault zone

  1. Progress integrating ID-TIMS U-Pb geochronology with accessory mineral geochemistry: towards better accuracy and higher precision time

    NASA Astrophysics Data System (ADS)

    Schoene, B.; Samperton, K. M.; Crowley, J. L.; Cottle, J. M.

    2012-12-01

    It is increasingly common that hand samples of plutonic and volcanic rocks contain zircon with dates that span between zero and >100 ka. This recognition comes from the increased application of U-series geochronology on young volcanic rocks and the increased precision to better than 0.1% on single zircons by the U-Pb ID-TIMS method. It has thus become more difficult to interpret such complicated datasets in terms of ashbed eruption or magma emplacement, which are critical constraints for geochronologic applications ranging from biotic evolution and the stratigraphic record to magmatic and metamorphic processes in orogenic belts. It is important, therefore, to develop methods that aid in interpreting which minerals, if any, date the targeted process. One promising tactic is to better integrate accessory mineral geochemistry with high-precision ID-TIMS U-Pb geochronology. These dual constraints can 1) identify cogenetic populations of minerals, and 2) record magmatic or metamorphic fluid evolution through time. Goal (1) has been widely sought with in situ geochronology and geochemical analysis but is limited by low-precision dates. Recent work has attempted to bridge this gap by retrieving the typically discarded elution from ion exchange chemistry that precedes ID-TIMS U-Pb geochronology and analyzing it by ICP-MS (U-Pb TIMS-TEA). The result integrates geochemistry and high-precision geochronology from the exact same volume of material. The limitation of this method is the relatively coarse spatial resolution compared to in situ techniques, and thus averages potentially complicated trace element profiles through single minerals or mineral fragments. In continued work, we test the effect of this on zircon by beginning with CL imaging to reveal internal zonation and growth histories. This is followed by in situ LA-ICPMS trace element transects of imaged grains to reveal internal geochemical zonation. The same grains are then removed from grain-mount, fragmented, and

  2. Solids sampling using double-pulse laser ablation inductivelycoupled plasma mass spectrometry

    SciTech Connect

    Gonzalez, Jhanis; Liu, Chunyi; Yoo, Jong; Mao, Xianglei; Russo,RickRick

    2003-07-01

    This paper describes the use of double-pulse laser ablation to improve ICP-MS internal precision (temporal relative standard deviation, %TRSD). Double pulse laser ablation offers reduced fractionation, increased sensitivity, and improved signal to noise ratios. The first pulse is used to ablate a large quantity of mass from the sample surface. The second pulse is applied with a variable time delay after the first pulse to break the ablated mass into a finer aerosol, which is more readily transported to and digested in the ICP-MS.

  3. Thermal and exhumation history of the central Tianshan (NW China): Constraints by U-Pb geochronology and Ar-Ar and (U-Th)/He thermochronology

    NASA Astrophysics Data System (ADS)

    Yin, J.; Chen, W.; Hodges, K. V.; Xiao, W.; Van Soest, M. C.; Cai, K.; Zhang, B.; Mercer, C. M.; Yuan, C.

    2015-12-01

    Geochronology and thermochronology using multiple mineral-isotopic chronometers reveals the thermo-tectonic history of the central Tianshan (NW China) from emplacement to exhumation. Granites from the central Tianshan, which are associated with the southward subduction of the northern Tianshan Ocean, have been dated at 362-354 Ma using the LA-ICP-MS Zircon U-Pb method. A younger diorite sample (282 ± 1 Ma, Zircon U-Pb method by LA-ICP-MS) from northern Tianshan formed during the final closure of the Northern Tianshan Ocean when the Junggar Block collided with the Yili-Central Tianshan Block. 40Ar/39Ar step-wise heating plateau dates (biotite Ar/Ar: 312-293 Ma; Plagioclase Ar/Ar: 270-229 Ma) from the Central Tianshan show rapid post-magmatic cooling during the Late Carboniferous-Early Permian followed by a more modest rate of cooling from the middle Permian to the middle Jurassic. The northern Tianshan diorite (biotite Ar/Ar: 240 ± 1 Ma) also reveals a middle Jurassic cooling. Apatite (U-Th )/He dates from the central Tianshan samples range from ca. 130 Ma to ca. 116 Ma. The Apatite (U-Th )/He date for the northern Tianshan sample is ca. 27 Ma. Previous studies also reported Apatite (U-Th)/He ages of ca. 44 Ma-11 Ma in the Baluntai area of the southern Central Tianshan[1]. Two episodes of cooling are distinguished by thermal history modelling: (1) Mesozoic cooling occurred as the result of the exhumation and tectonic reactivation of the central Tianshan; and (2) The Tianshan orogenic belt has been rapidly exhumed since the Middle Cenozoic. References [1] Lü, H.H., Chang, Y., Wang, W., Zhou, Z.Y., 2013. Rapid exhumation of the Tianshan Mountains since the early Miocene: Evidence from combined apatite fission track and (U-Th)/He thermochronology. Science China: Earth Sciences, 43(12): 1964-1974 (in Chinese).

  4. Time-resolved ICP-MS measurement: a new method for elemental and multiparametric analysis of single cells.

    PubMed

    Miyashita, Shin-ichi; Groombridge, Alexander S; Fujii, Shin-ichiro; Takatsu, Akiko; Chiba, Koichi; Inagaki, Kazumi

    2014-01-01

    Time-resolved inductively coupled plasma mass spectrometry (ICP-MS) has attracted much attention for elemental and multiparametric analysis of single cells, instead of a classical bulk analysis of large amount of cells after a dissolution. In the time-resolved measurement, cells are directly introduced into the plasma via nebulizing or micro drop dispensing, and then ion plumes corresponding to single cells are individually detected with a high time resolution. The sensitivity and cell throughput in the measurement strongly depend on the time resolution. A high cell introduction efficiency into the plasma supports for a reduction of cell consumption. Biomolecules can also be measured through the attachment of elemental tags, and then the amount distribution of elements and biomolecules in single cells can be evaluated, while providing information concerning cell-to-cell variations. By applying ICP time-of-flight mass spectrometry (ICP-TOFMS), multiparametric analysis of elements and biomolecules can be achieved similar to that by a flow cytometer. This article highlights the technical aspects of the time-resolved ICP-MS measurement technique for elemental and multiparametric analysis of single cells.

  5. Feasibility of microwave-induced combustion for trace element determination in Engraulis anchoita by ICP-MS.

    PubMed

    Maciel, Juliana V; Knorr, Camila L; Flores, Erico M M; Müller, Edson I; Mesko, Marcia F; Primel, Ednei G; Duarte, Fabio A

    2014-02-15

    A method based on microwave-induced combustion (MIC) was developed for fish (Engraulis anchoita) digestion and subsequent determination of As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Se, and Zn by inductively coupled plasma mass spectrometry (ICP-MS). A reflux step (5 min) was applied to improve absorption and recovery of analytes. Nitric acid was investigated as absorbing solution and suitable results were achieved using 5 mol L⁻¹ HNO₃. Microwave-assisted digestion in closed vessels using concentrated HNO₃ was also evaluated for comparison of results. Both sample preparation methods were considered suitable for sample digestion but MIC was preferable not only because diluted HNO3 can be used as absorbing solution but also because it provides higher efficiency of digestion and also better limits of detection. Accuracy was evaluated by the analysis of certified reference materials (DORM-2 and TORT-2) after MIC digestion with subsequent determination by ICP-MS. Agreement with certified values was better than 94%. PMID:24128565

  6. Isotopic signature of selected lanthanides for nuclear activities profiling using cloud point extraction and ICP-MS/MS.

    PubMed

    Labrecque, Charles; Lebed, Pablo J; Larivière, Dominic

    2016-05-01

    The presence of fission products, which include numerous isotopes of lanthanides, can impact the isotopic ratios of these elements in the environment. A cloud point extraction (CPE) method was used as a preconcentration/separation strategy prior to measurement of isotopic ratios of three lanthanides (Nd, Sm, and Eu) by inductively coupled plasma tandem mass spectrometry (ICP-MS/MS). To minimise polyatomic interference, the combination of interferents removal by CPE, reaction/collision cell conditions in He and NH3 mode and tandem quadrupole configuration was investigated and provided optimal results for the determination of isotopic ratio in environmental samples. Isotopic ratios were initially measured in San Joaquin soil (NIST-2709a), an area with little contamination of nuclear origin. Finally, samples collected from three sites with known nuclear activities (Fangataufa Lagoon in French Polynesia, Chernobyl and the Ottawa River near Chalk River Laboratory) were analysed and all exhibited altered isotopic ratios for (143/145)Nd, (147/149)Sm, and (151/153)Eu. These results demonstrate the potential of CPE and ICP-MS/MS for the detection of altered isotopic ratio in environmental samples collected in area subjected to nuclear anthropogenic contamination. The detection of variations in these isotopic ratios of fission products represents the first application of CPE in nuclear forensic investigations of environmental samples. PMID:26895346

  7. [Determination of Sb and Bi in 24 international geological reference materials by using pressurized acid digestion-ICP-MS].

    PubMed

    Hu, Zhao-chu; Gao, Shan; Liu, Xiao-ming; Yuan, Hong-lin; Liu, Ye; Diwu, Chun-rong

    2007-12-01

    The authors studied in detail the memory effect of Bi, Sb, As and Te in ICP-MS. The produced memory effects of these element were in the order of Bi>Sb>Te>As. Bi was seriously adsorbed by the polypropylene sample storing bottle and the sample introduction system in the low nitric acid medium (0.01%-1% HNO3). The washout effect of 0.1% HF was found to be better than those of 6% HNO3 and 0.1% HClO4. Under the given experiment conditions, the instrumental limit of detection was 0.001 and 0.0001 ng x mL(-1) for Sb and Bi, respectively. The authors report the determination of Sb and Bi in 24 international geological reference materials by using pressurized acid digestion-ICP-MS (including AGV-2, BHVO-2, BCR-2, etc.). Most of the results were found to be in reasonable agreement with the reported values in the literature. The authors' determined values of Sb for GSR-1 (granite; 0.30 microg x g(-1)) and JP-1 (peridotite; 0.045 microg x g(-1)) are obviously higher than those reported values. This is attributed to the efficient pressurized acid digestion, which is generally much more efficient than conventional wet digestions for insoluble minerals. PMID:18330312

  8. Rapid speciation and quantification of selenium compounds by HPLC-ICP MS using multiple standards labelled with different isotopes.

    PubMed

    Ohta, Yuki; Suzuki, Noriyuki; Kobayashi, Yayoi; Hirano, Seishiro

    2011-09-01

    Speciation analysis using high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP MS) is now commonly used to investigate metabolic and toxicological aspects of some metals and metalloids. We have developed a rapid method for simultaneous identification and quantification of metabolites of selenium (Se) compounds using multiple standards labelled with different isotopes. A mixture of the labelled standards was spiked in a selenised garlic extract and the sample was subjected to speciation analysis by HPLC-ICP MS. The selenised garlic contains γ-glutamyl-methylselenocysteine, methylselenocysteine, and selenomethionine and the concentrations of those Se compounds were 723.8, 414.8, and 310.7 ng Se ml(-1), respectively. The isotopically labelled standards were also applied to the speciation of Se in rat urine. Selenate, methylselenonic acid, selenosugar, and trimethyselenium ions were found to be excreted by the present speciation procedure. Multiple standards labelled with different stable isotopes enable high-throughput identification and quantitative measurements of Se metabolites.

  9. 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.

  10. Determination of (187)Os in molybdenite by ICP-MS with neutron-induced (186)Os and (188)Os spikes.

    PubMed

    Qu, W; Du, A; Zhao, D

    2001-10-31

    The article describes a method for the determination of (187)Os in molybdenite by isotope dilution inductively coupled plasma-mass spectrometry (ID-ICP-MS) with neutron-induced (186)Os and (188)Os spike. The spike used in the present work was prepared in line with the principle by which artificial nuclides are produced in a nuclear reaction. The concentration and isotopic composition of osmium in the prepared spike were evaluated accurately with the isotope dilution method, using negative thermal ion mass spectrometry (N-TIMS). The advantage of this method is that using (186)Os and (188)Os double spikes can effectively compensate for the mass discrimination effects of ICP-MS. Thus, the common correction practice for mass bias in the isotope dilution method with a single spike is unnecessary. In addition, the method enables one to reduce the determined error arising from instrumental instability. The precision for the (187)Os/((186)Os+(188)Os) ratio was approximately 2% (2sigma, RSD), but in the case of (187)Os/(186)Os, (187)Os/(188)Os and (186)Os/(188)Os, precision ranged from 2.0 to 8% (2sigma, RSD). The results for (187)Os concentration in a molybdenite sample determined with this method showed good agreement with reference values.

  11. Speciation of small molecules and inorganic ions in salmon egg cell cytoplasm by surfactant-mediated HPLC/ICP-MS.

    PubMed

    Matsuura, Hirotaka; Hasegawa, Takuya; Nagata, Hitomi; Takatani, Kohei; Asano, Motoki; Itoh, Akihide; Haraguchi, Hiroki

    2003-01-01

    The speciation of diverse elements in salmon egg cell cytoplasm was performed by a surfactant-mediated HPLC/ICP-MS hyphenated system. In the present experiment, an ODS column coated with CHAPS (3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate), which is a zwitterionic bile acid derivative, was employed as a surfactant-mediated separation column, and ICP-MS was used as an element-selective detector. The present surfactant-mediated HPLC allowed us to separate large and small molecules within 10 min; large molecules, such as proteins, were eluted within 2.5 min, while small molecules were eluted after 2.5 min, but within 10 min. In the present experiment, Fe, Cu, and Zn in egg cell cytoplasm were observed mostly in species with large molecular weights, indicating that these elements are contained as metalloproteins or metalloenzymes in egg cell cytoplasm. On the contrary, it was found that P, S, Mo, and halogens in egg cell cytoplasm were contained as small molecules or inorganic ions. The major species of P in egg cell cytoplasm was identified as the phosphate ion (PO4(3-)). Molybdenum, Cl, and Br in egg cell cytoplasm were molybdate (MoO4(2-), chloride (Cl-), and bromide (Br-) ions, respectively.

  12. Chromium and its speciation in water samples by HPLC/ICP-MS--technique establishing metrological traceability: a review since 2000.

    PubMed

    Markiewicz, Barbara; Komorowicz, Izabela; Sajnóg, Adam; Belter, Magdalena; Barałkiewicz, Danuta

    2015-01-01

    Chromium holds a special position among living organisms because depending on its species it can be either essential or toxic. Cr(VI) even at very low concentrations is harmful and carcinogenic, while Cr(III) is a necessary microelement for cellular metabolism. Therefore, a simple analysis of Cr concentration in collected samples will not be able to distinguish these differences effectively: for a proper chemical analysis we need to perform a reliable detection and quantification of Cr species. Separation and detection of chromium can be accomplished with high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC/ICP-MS) in a one-step. Our review assembles articles published since 2000 regarding chromium speciation in water samples with the use of HPLC/ICP-MS. It addresses the following issues: chromium chemistry, the possibilities of dealing with interferences, metrological aspects, analytical performance and speciated isotope dilution mass spectrometry (SIDMS) which is a definitive measurement method. The authors would like to advocate this hyphenated advanced technique as well as the metrological approach in speciation analysis of chromium.

  13. Elemental fingerprinting of soils using ICP-MS and multivariate statistics: a study for and by forensic chemistry majors.

    PubMed

    Reidy, Lorlyn; Bu, Kaixuan; Godfrey, Murrell; Cizdziel, James V

    2013-12-10

    Students in an instrumental analysis course with a forensic emphasis were presented with a mock scenario in which soil was collected from a murder suspect's car mat, from the crime scene, from adjacent areas, and from more distant locations. Students were then asked to conduct a comparative analysis using the soil's elemental distribution fingerprints. The soil was collected from Lafayette County, Mississippi, USA and categorized as sandy loam. Eight student groups determined twenty-two elements (Li, Be, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Cs, Ba, Pb, U) in seven samples of soil and one sample of sediment by microwave-assisted acid digestion and inductively coupled plasma-mass spectrometry (ICP-MS). Data were combined and evaluated using multivariate statistical analyses. All eight student groups correctly classified their unknown among the different locations. Students learn, however, that whereas their results suggest that the elemental fingerprinting approach can be used to distinguish soils from different land-use areas and geographic locations, applying the methodology in forensic investigations is more complicated and has potential pitfalls. Overall, the inquiry-based pedagogy enthused the students and provided learning opportunities in analytical chemistry, including sample preparation, ICP-MS, figures-of-merit, and multivariate statistics.

  14. Determination of gallium originated from a gallium-based anticancer drug in human urine using ICP-MS.

    PubMed

    Filatova, Darya G; Seregina, Irina F; Foteeva, Lidia S; Pukhov, Vladimir V; Timerbaev, Andrei R; Bolshov, Mikhail A

    2011-05-01

    Urine analysis gives an insight into the excretion of the administered drug which is related to its reactivity and toxicity. In this work, the capability of inductively coupled plasma mass spectrometry (ICP-MS) to measure ultratrace metal levels was utilized for rapid assaying of gallium originating from the novel gallium anticancer drug, tris(8-quinolinolato)gallium(III) (GaQ(3)), in human urine. Sample dilution with 1% (v/v) HNO(3) as the only required pre-treatment was shown to prevent contamination of the sample introduction system and to reduce polyatomic interferences from sample components. The origin of the blank signal at masses of gallium isotopes, 71 and 69, was investigated using high-resolution ICP-MS and attributed, respectively, to the formation of (36)Ar(35)Cl(+) and (40)Ar(31)P(+) ions and, tentatively, to a triplet of doubly charged ions of Ba, La, and Ce. The accuracy and precision performance was tested by evaluating a set of parameters for analytical method validation. The developed assay has been applied for the determination of gallium in urine samples spiked with GaQ(3). The achieved recoveries (95-102%) and quantification limit of 0.2 μg L(-1) emphasize the practical applicability of the presented analytical approach to monitor renal elimination of GaQ(3) at all dose levels in clinical trials that are currently in progress.

  15. Isotopic signature of selected lanthanides for nuclear activities profiling using cloud point extraction and ICP-MS/MS.

    PubMed

    Labrecque, Charles; Lebed, Pablo J; Larivière, Dominic

    2016-05-01

    The presence of fission products, which include numerous isotopes of lanthanides, can impact the isotopic ratios of these elements in the environment. A cloud point extraction (CPE) method was used as a preconcentration/separation strategy prior to measurement of isotopic ratios of three lanthanides (Nd, Sm, and Eu) by inductively coupled plasma tandem mass spectrometry (ICP-MS/MS). To minimise polyatomic interference, the combination of interferents removal by CPE, reaction/collision cell conditions in He and NH3 mode and tandem quadrupole configuration was investigated and provided optimal results for the determination of isotopic ratio in environmental samples. Isotopic ratios were initially measured in San Joaquin soil (NIST-2709a), an area with little contamination of nuclear origin. Finally, samples collected from three sites with known nuclear activities (Fangataufa Lagoon in French Polynesia, Chernobyl and the Ottawa River near Chalk River Laboratory) were analysed and all exhibited altered isotopic ratios for (143/145)Nd, (147/149)Sm, and (151/153)Eu. These results demonstrate the potential of CPE and ICP-MS/MS for the detection of altered isotopic ratio in environmental samples collected in area subjected to nuclear anthropogenic contamination. The detection of variations in these isotopic ratios of fission products represents the first application of CPE in nuclear forensic investigations of environmental samples.

  16. Enantioselective determination of thyroxine enantiomers by ligand-exchange CE with UV absorbance and ICP-MS detection.

    PubMed

    Kang, Jianzhen; Kutscher, Daniel; Montes-Bayón, Maria; Blanco-González, Elisa; Sanz-Medel, Alfredo

    2009-05-01

    A simple CE method has been developed for the separation and determination of thyroxine (T4) enantiomers in pharmaceutical formulations. The method was based on ligand-exchange mechanism using a Cu(II)/L-proline complex as chiral selector. The effects of different parameters affecting separation such as chiral selector concentration, organic additive, buffer pH and temperature were investigated. A baseline separation of the two enantiomers was obtained at a Cu(II)/L-proline ratio of 1:8 in a borate buffer (15 mmol/L, pH 9.6) containing 10% v/v acetonitrile. Under the optimized conditions, precision linearity range and detection limits of the developed enantioselective CE method were evaluated and compared using two different detection systems: conventional UV detection at 226 nm and iodine (127I)specific detection ("chiral speciation") with ICP-MS. Both methodologies show adequate analytical performance characteristics with detection limits around 0.30 microg/mL for each enantiomer of T4. Finally, a levothroid pharmaceutical formulation sample was successfully analyzed using both developed methods CE-UV and CE-ICP-MS.

  17. Feasibility of microwave-induced combustion for trace element determination in Engraulis anchoita by ICP-MS.

    PubMed

    Maciel, Juliana V; Knorr, Camila L; Flores, Erico M M; Müller, Edson I; Mesko, Marcia F; Primel, Ednei G; Duarte, Fabio A

    2014-02-15

    A method based on microwave-induced combustion (MIC) was developed for fish (Engraulis anchoita) digestion and subsequent determination of As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Se, and Zn by inductively coupled plasma mass spectrometry (ICP-MS). A reflux step (5 min) was applied to improve absorption and recovery of analytes. Nitric acid was investigated as absorbing solution and suitable results were achieved using 5 mol L⁻¹ HNO₃. Microwave-assisted digestion in closed vessels using concentrated HNO₃ was also evaluated for comparison of results. Both sample preparation methods were considered suitable for sample digestion but MIC was preferable not only because diluted HNO3 can be used as absorbing solution but also because it provides higher efficiency of digestion and also better limits of detection. Accuracy was evaluated by the analysis of certified reference materials (DORM-2 and TORT-2) after MIC digestion with subsequent determination by ICP-MS. Agreement with certified values was better than 94%.

  18. [Study on phase distribution and release of heavy metal in pyrite using sequential extraction procedure and ICP-MS].

    PubMed

    Zhang, Ping; Qi, Jian-Ying; Yang, Chun-Xia; Chen, Yong-Heng

    2007-06-01

    Heavy metal elements of V, Cr, Mn, Co, Ni, Cu, Zn, Sr, Mo, Cd, Sb, Ba and Pb were determined by ICP-MS. The linear ranges of determination for these elements were obtained, and the correlation coefficients were larger than 0.997. The detection limit ranges were from 0.005 to 0.01 microg x L(-1) and the RSDs were lower than 5%. Phase distributions of heavy metals in pyrite were analyzed by ICP-MS with sequential extraction procedure. The result showed that Pb was the main heavy metal in pyrite and its total content was 830 mg x kg(-1). Pb existed mostly in carbonate or galena (PbS) phase of pyrite and the proportion was 56.9%. Pb existed less in iron oxides with 29.7% in proportion, and least in sulfide and silicate with 3.5% and 9.9%, respectively. The release of Pb in pyrite was primary in natural environment, but the release of Cr and Cd was not be ignorable, too. PMID:17763794

  19. [Determination of Sb and Bi in 24 international geological reference materials by using pressurized acid digestion-ICP-MS].

    PubMed

    Hu, Zhao-chu; Gao, Shan; Liu, Xiao-ming; Yuan, Hong-lin; Liu, Ye; Diwu, Chun-rong

    2007-12-01

    The authors studied in detail the memory effect of Bi, Sb, As and Te in ICP-MS. The produced memory effects of these element were in the order of Bi>Sb>Te>As. Bi was seriously adsorbed by the polypropylene sample storing bottle and the sample introduction system in the low nitric acid medium (0.01%-1% HNO3). The washout effect of 0.1% HF was found to be better than those of 6% HNO3 and 0.1% HClO4. Under the given experiment conditions, the instrumental limit of detection was 0.001 and 0.0001 ng x mL(-1) for Sb and Bi, respectively. The authors report the determination of Sb and Bi in 24 international geological reference materials by using pressurized acid digestion-ICP-MS (including AGV-2, BHVO-2, BCR-2, etc.). Most of the results were found to be in reasonable agreement with the reported values in the literature. The authors' determined values of Sb for GSR-1 (granite; 0.30 microg x g(-1)) and JP-1 (peridotite; 0.045 microg x g(-1)) are obviously higher than those reported values. This is attributed to the efficient pressurized acid digestion, which is generally much more efficient than conventional wet digestions for insoluble minerals.

  20. Laser-Ablation ICP-MS Analyses of Meteoritic Metal Grains in Lunar Impact-Melt Breccias

    NASA Technical Reports Server (NTRS)

    Korotev, R. L.; Jolliff, B. L.; Campbell, A. J.; Humayun, M.

    2003-01-01

    Lunar impact-melt breccias contain metal grains from the meteorites that formed the breccias. Because the breccias contain clastic material that may derive from older breccias, metal grains from earlier impacts may be present, too. The large subset of moderately mafic (8 - 12% FeO), KREEP-rich ("LKFM") melt breccias is particularly important because: (1) these are the melt breccias most likely to have been produced in basin-forming impacts, (2) it is from these breccias that many of the approx. 3.9 Gyr ages that are so common in lunar samples derive, (3) the breccias contain large proportions of FeNi metal, more than 1% in some types of Apollo 16 breccias, and (4) the metal potentially provides information about the impactors causing the apparent cataclysm at 3.9 Gyr.

  1. Precise and accurate measurement of U and Th isotopes via ICP-MS using a single solution

    NASA Astrophysics Data System (ADS)

    Mertz-Kraus, R.; Sharp, W. D.; Ludwig, K. R.

    2012-04-01

    U-series isotope measurements by ICP-MS commonly utilize separate runs for U and Th and standard-sample bracketing to determine correction factors for mass fractionation and ion counter yields. Here we present an approach where all information necessary to calculate an age (aside from background/baseline levels) is determined while analyzing a single solution containing both U and Th. This internally calibrated procedure should reduce any bias caused by distinct behavior of sample versus standard solutions during analysis and offers advantages including simplicity of operation, calculation of preliminary ages in real time, and simplified analysis of errors and their sources. Hellstrom (2003) developed a single-solution, internally-calibrated technique for an ICP-MS with multiple ion counters, but to our knowledge no such technique is available for an ICP-MS with a single ion counter. We use a Thermo Neptune Plus multi-collector ICP-MS with eight movable Faraday cups and a fixed center cup/ion counter equipped with a high abundance-sensitivity filter (RPQ). We use Faraday cups to measure all masses except 230 and 234, which are measured on the ion counter with the RPQ detuned (i.e., Suppressor voltage = 9950 V). 238U is maintained in a cup throughout the analysis to avoid reflections and is used to normalize signal instabilities related to sample introduction. Each analysis has a three-part structure, i.e. 1) background/baseline levels, 2) sample composition, and 3) peak-tails are sequentially determined. In step 1, multiplier dark noise/Faraday baselines plus background intensities at each mass are determined while aspirating running solution. During sample measurement in step 2, ion counter yields for Th and U are determined using signals of 300-400 kcps for 229Th and 233U by measuring 229Th/238U and 233U/238U ratios first with the minor masses on the ion counter and then with both masses in cups. Mass bias can be determined using the 233U/236U ratio of the spike

  2. LA-ICP-MS heavy metal analyses of fish scales from sediments of the Oxbow Lake Certak of the Morava River (Czech Republic)

    NASA Astrophysics Data System (ADS)

    Holá, M.; Kalvoda, J.; Bábek, O.; Brzobohatý, R.; Holoubek, I.; Kanický, V.; Skoda, R.

    2009-07-01

    Heavy metal concentrations were studied in the scales of recent and subrecent (2-25 years old) fish buried in the oxbow lake sediments of the Morava River. The samples were taken from two cores up to 4-m deep and analysed using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and an electron microprobe analysis (EMPA). The results were compared with heavy metal concentrations of bulk samples of the embedding sediment. The study has revealed substantial differences in heavy metal contents existing between the recent and subrecent fish scales documenting an extreme rapidity of the diagenesis/fossilization processes. The most apparent features of the early fossilization include the quick loss of the mucous envelope, collagen and magnesium and an enormous increase in the heavy metal concentrations in particular iron, which is connected with a colour change. The variations in heavy metal contents in fish scales within a sample are attributed to variations in heavy metal content in the environment and variable amounts of organic matter in the embedding sediment. In contrast to the contamination of the embedding sediment, no general increase in heavy metal concentrations in fish scales was observed down to the cores. It is inferred that the rapid sorption stabilizes the biologic hydroxyapatite of the fish scales, which thus rapidly attain a thermodynamic equilibrium with the embedding water-saturated sediment. The results show that the processes of sorption, fossilization and stabilization of hydroxyapatite can act very quickly over a time scale of several years and represent thus a great advantage in the preservation of the original signals of the ancient environments.

  3. Liquid immiscibility between arsenide and sulfide melts: evidence from a LA-ICP-MS study in magmatic deposits at Serranía de Ronda (Spain)

    NASA Astrophysics Data System (ADS)

    Piña, R.; Gervilla, F.; Barnes, S.-J.; Ortega, L.; Lunar, R.

    2015-03-01

    The chromite-Ni arsenide (Cr-Ni-As) and sulfide-graphite (S-G) deposits from the Serranía de Ronda (Málaga, South Spain) contain an arsenide assemblage (nickeline, maucherite and nickeliferous löllingite) that has been interpreted to represent an arsenide melt and a sulfide-graphite assemblage (pyrrhotite, pentlandite, chalcopyrite and graphite) that has been interpreted to represent a sulfide melt, both of which have been interpreted to have segregated as immiscible liquids from an arsenic-rich sulfide melt. We have determined the platinum-group element (PGE), Au, Ag, Se, Sb, Bi and Te contents of the arsenide and sulfide assemblages using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to establish their partitioning behaviour during the immiscibility of an arsenide melt from a sulfide melt. Previous experimental work has shown that PGE partition more strongly into arsenide melts than into sulfide melts and our results fit with this observation. Arsenide minerals are enriched in all PGE, but especially in elements with the strongest affinity for the arsenide melt, including Ir, Rh and Pt. In contrast and also in agreement with previous studies, Se and Ag partition preferentially into the sulfide assemblage. The PGE-depleted nature of sulfides in the S-G deposits along with the discordant morphologies of the bodies suggest that these sulfides are not mantle sulfides, but that they represent the crystallization product of a PGE-depleted sulfide melt due to the sequestering of PGE by an arsenide melt.

  4. Significance of zircon U-Pb ages from the Pescadero felsite, west-central California coast ranges

    USGS Publications Warehouse

    McLaughlin, Robert J.; Moore, Diane E.; ,; Martens, UWE C.; Clark, J.C.

    2011-01-01

    Weathered felsite is associated with the late Campanian–Maastrichtian Pigeon Point Formation near Pescadero, California. Poorly exposed, its age and correlation are uncertain. Is it part of the Pigeon Point section west of the San Gregorio–Hosgri fault? Does it rest on Nacimiento block basement? Is it dextrally offset from the Oligocene Cambria Felsite, ∼185 km to the southeast? Why is a calc-alkaline hypabyssal igneous rock intrusive into the outboard accretionary prism? To address these questions, we analyzed 43 oscillatory-zoned zircon crystals from three incipiently recrystallized pumpellyite ± prehnite ± laumontite-bearing Pescadero felsite samples by sensitive high-resolution ion microprobe–reverse geometry (SHRIMP-RG) and laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) techniques. Thirty-three zircons gave late Mesozoic U-Pb ages, with single-grain values ranging from 81 to 167 Ma; ten have pre-Mesozoic, chiefly Proterozoic ages. A group of the four youngest Pescadero zircons yielded an apparent maximum igneous age of ca. 86–90 Ma. Reflecting broad age scatter and presence of partly digested sandstone inclusions, we interpret the rest of the zircons (perhaps all) as xenocrysts. Twenty-three zircons were separated and analyzed from two samples of the similar Cambria Felsite, yielding a unimodal 27 Ma U-Pb age. Clearly, the origin of the Upper Oligocene Cambria Felsite is different from that of the Upper Cretaceous Pescadero felsite; these rocks are not correlated, and do not constrain displacement along the San Gregorio–Hosgri fault. Peak ages differ slightly, but relative probability curves for Mesozoic and pre-Mesozoic Pescadero zircons compare well, for example, with abundant U-Pb age data for detrital zircons from Franciscan metaclastic strata ∼100 km to the east in the Diablo Range–San Francisco Bay area, San Joaquin Great Valley Group turbidites, Upper Cretaceous Nacimiento block Franciscan strata, and Upper

  5. Feasibility of asymmetric flow field-flow fractionation coupled to ICP-MS for the characterization of wear metal particles and metalloproteins in biofluids from hip replacement patients.

    PubMed

    Loeschner, Katrin; Harrington, Chris F; Kearney, Jacque-Lucca; Langton, David J; Larsen, Erik H

    2015-06-01

    Hip replacements are used to improve the quality of life of people with orthopaedic conditions, but the use of metal-on-metal (MoM) arthroplasty has led to poor outcomes for some patients. These problems are related to the generation of micro- to nanosized metal wear particles containing Cr, Co or other elements, but the current analytical methods used to investigate the processes involved do not provide sufficient information to understand the size or composition of the wear particles generated in vivo. In this qualitative feasibility study, asymmetric flow field-flow fractionation (AF(4)) coupled with inductively coupled plasma mass spectrometry (ICP-MS) was used to investigate metal protein binding and the size and composition of wear metal particles present in serum and hip aspirates from MoM hip replacement patients. A well-established HPLC anion exchange chromatography (AEC) separation system coupled to ICP-MS was used to confirm the metal-protein associations in the serum samples. Off-line single particle ICP-MS (spICP-MS) analysis was used to confirm the approximate size distribution indicated by AF(4) of the wear particles in hip aspirates. In the serum samples, AF(4) -ICP-MS suggested that Cr was associated with transferrin (Tf) and Co with albumin (Alb) and an unidentified species; AEC-ICP-MS confirmed these associations and also indicated an association of Cr with Alb. In the hip aspirate sample, AF(4)-ICP-MS suggested that Cr was associated with Alb and Tf and that Co was associated with Alb and two unidentified compounds; AEC analysis confirmed the Cr results and the association of Co with Alb and a second compound. Enzymatic digestion of the hip aspirate sample, followed by separation using AF(4) with detection by UV absorption (280 nm), multi-angle light scattering and ICP-MS, suggested that the sizes of the Cr-, Co- and Mo-containing wear particles in a hip aspirate sample were in the range 40-150 nm. Off-line spICP-MS was used to confirm these

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  7. Determination of Trace Cadmium in Geological Samples by Aerosol Dilution ICP-MS with Inverse Aqua Regia Extraction

    NASA Astrophysics Data System (ADS)

    Xu, Q.; Guo, W.; Jin, L.; Hu, S.; Chai, X.

    2015-12-01

    Cadmium (Cd) is a trace element that occurs at ppb level in most terrestrial materials. The determination of Cd in geological samples by ICP-MS is subject to Zr and/or Mo based oxide/hydroxide interference. This study developed a valid method for the determination of Cd by Ar aerosol dilution ICP-MS with inverse aqua regia extraction (in a water bath at 95℃ for 2h). An Agilent 7700x ICP-MS (Agilent Technologies, USA) with an aerosol dilution system was used. The extraction procedure separated most of the Zr matrix (>90%) from the analyte, and the residual Zr- hydroxides and Mo-oxides or hydroxides were successfully eliminated by adding an amount of Ar to the sample aerosol prior to the plasma. Compared to the conventional operation, the amounts of oxide and hydroxide ions formed in the plasma were reduced by up to 10 times. The relative yields of the interfering oxides and hydroxides were as low as 0.012% ((94Mo16OH++95Mo16O+)/(94Mo++95Mo+)) and 0.007% (94Zr16OH+/94Zr+). Under the optimized dilution gas flow rate (0.85 L min-1) and carrier gas flow rate (0.24 L min-1), the limit of detection (LOD, 3s) for 111Cd was 1.3 ng g-1. The accuracy of the method was assessed by using two USGS SRMs (andesite AGV-2 and basalt BCR-2). The Cd contents determined for AGV-2 and BCR-2 are 0.058±0.004μg g-1 and 0.148±0.007μg g-1 (N=10), which are in good agreement with the USGS reference values (0.061μg g-1 and 0.14μg g-1). The proposed method was also applied to determine Cd contents in 65 IGGE SRMs (28 soils, 28 sediments and 9 rocks). The measured Cd levels in these samples agree well with their certified values. The developed method shows great potential for the direct determination of trace levels of Cd in geological samples.

  8. Evaluation of bromine and iodine content of milk whey proteins combining digestion by microwave-induced combustion and ICP-MS determination.

    PubMed

    da Silva, Sabrina Vieira; Picoloto, Rochele Sogari; Flores, Erico Marlon Moraes; Wagner, Roger; dos Santos Richards, Neila Silvia Pereira; Barin, Juliano Smanioto

    2016-01-01

    The bromine and iodine content of whey protein concentrate (WPC), hydrolysate (WPH), and isolate (WPI) was evaluated combining microwave-induced combustion (MIC) digestion with inductively coupled plasma mass spectrometry (ICP-MS) determination. MIC digestion allowed the decomposition of up to 500 mg of samples using diluted NH4OH solution (25 mmol L(-1)) for absorption of analytes, assuring the compatibility with ICP-MS determination. Accuracy was evaluated using milk powder certified reference material (NIST 8435) with good agreements for Br and I (102% and 105%, respectively). For Br and I, the limit of quantification obtained by ICP-MS was 7 and 281 times lower in comparison with ion chromatography determination, respectively. Iodine could be enriched in whey protein production and up to 70% of the tolerable upper intake level was found, thus revealing the need to monitor it in whey proteins. On the other hand, the concentration of Br was below its acceptable daily intake.

  9. Provenance and sediment dynamics within river basins in Western Peru through detrital zircons U-Pb ages

    NASA Astrophysics Data System (ADS)

    Camille, Litty; Pierre, Lanari; Marco, Burn; Fritz, Schlunegger

    2016-04-01

    U-Pb dating of detrital zircons from clastic sediments by LA-ICPMS has become a popular method in sedimentary correlation and provenance studies. Because of remarkable durability, detrital zircons may be reworked through multiple sedimentary cycles and provide an ideal material to study the sedimentary provenance in rivers and the erosional characteristics. The Western side of the Peruvian Andes has experienced multiple pluvial periods induced phases of erosion and the formation of subsequent cut-and-fill terrace sequences since the Pleistocene. The aim of the study is to estimate the source areas of the terrace and modern deposits to infer changes in sediment dynamics through time and correlate them with the climatic change and especially precipitation patterns. To this extent, we determined the provenance of 4 dated terrace deposits along with modern sediments from the same streams by matching detrital-zircon ages with crystallization ages of source rocks. Age populations of detrital zircons are derived using U-Pb LA-ICP-MS analysis of about 50 zircons. Results show changes in the sediment provenance through time. Nowadays, sediment source areas are mainly located on the uppermost reach of the rivers whereas during the Pleistocene, sediment source areas were both located in the headwaters and along the middle reach of the rivers. These differences in terms of provenance could correlate with a change in precipitation locations and rates. Indeed a scenario where the locus of precipitation occurrence shifted from the middle reaches including the Altiplano during the past, to the Altiplano only as observed today, along with higher precipitation rates during the periods of terraces formation, offers an explanation to explain the erosional patterns recorded by detrital zircons.

  10. Late Paleozoic to Jurassic tectonic evolution of the Bogda area (northwest China): Evidence from detrital zircon U-Pb geochronology

    NASA Astrophysics Data System (ADS)

    Tang, Wenhao; Zhang, Zhicheng; Li, Jianfeng; Li, Ke; Chen, Yan; Guo, Zhaojie

    2014-06-01

    Since the Cenozoic, the Tian Shan is rejuvenated by crustal shortening related to the ongoing India-Asia collision. However, the tectonic process prior to the Cenozoic remains ambiguous, especially in the Bogda area of the eastern Tian Shan. The continuous Late Paleozoic-Mesozoic sequences in the Bogda area record abundant information about the basin-mountain interaction. U-Pb (LA-ICP-MS) dating of detrital zircons from seven sandstone samples from Permian to Jurassic was used to investigate the changes of provenance and basin-mountain interaction in the Bogda area. During the Permian, proximal and synchronous pyroclastic materials were the major source. The Late Paleozoic magmatic belt in the North Tian Shan (NTS) had gradually become one of the main sources by the Late Permian, which implies the uplift and exhumation in the NTS area. This is interpreted in terms of near-source sedimentation in basin developing in a post-orogenic extension setting. The large range of U-Pb ages of detrital zircons observed in the Early-Middle Jurassic sediments encompasses most of the available sources implying a wide drainage pattern developing on a rather flat topography. Re-emergence of the Early Permian peak in the spectrum implies that the Bogda Mountains has existed as a gentle positive relief and began to provide materials to the submountain regions. The southern Junggar Basin extended towards to the south and evolved as a passively subsiding basin from the Middle Triassic to the Middle Jurassic. However, the synchronous pyroclastic (tuff) and the exhumed late Paleozoic detrital materials from the uplifted Bogda Mountains were the major component of the Upper Jurassic sediments. Associated to the conglomerate in the Kalaza Formation, the basin-range evolution entered a compression uplift stage. The basin pattern evolution of the Bogda area is consistent with that of the southern Junggar Basin.

  11. In situ quantification of Br and Cl in minerals and fluid inclusions by LA-ICP-MS: a powerful tool to identify fluid sources

    USGS Publications Warehouse

    Hammerli, Johannes; Rusk, Brian; Spandler, Carl; Emsbo, Poul; Oliver, Nicholas H.S.

    2013-01-01

    Bromine and chlorine are important halogens for fluid source identification in the Earth's crust, but until recently we lacked routine analytical techniques to determine the concentration of these elements in situ on a micrometer scale in minerals and fluid inclusions. In this study, we evaluate the potential of in situ Cl and Br measurements by LA-ICP-MS through analysis of a range of scapolite grains with known Cl and Br concentrations. We assess the effects of varying spot sizes, variable plasma energy and resolve the contribution of polyatomic interferences on Br measurements. Using well-characterised natural scapolite standards, we show that LA-ICP-MS analysis allows measurement of Br and Cl concentrations in scapolite, and fluid inclusions as small as 16 μm in diameter and potentially in sodalite and a variety of other minerals, such as apatite, biotite, and amphibole. As a demonstration of the accuracy and potential of Cl and Br analyses by LA-ICP-MS, we analysed natural fluid inclusions hosted in sphalerite and compared them to crush and leach ion chromatography Cl/Br analyses. Limit of detection for Br is ~8 μg g−1, whereas relatively high Cl concentrations (> 500 μg g−1) are required for quantification by LA-ICP-MS. In general, our LA-ICP-MS fluid inclusion results agree well with ion chromatography (IC) data. Additionally, combined cathodoluminescence and LA-ICP-MS analyses on natural scapolites within a well-studied regional metamorphic suite in South Australia demonstrate that Cl and Br can be quantified with a ~25 μm resolution in natural minerals. This technique can be applied to resolve a range of hydrothermal geology problems, including determining the origins of ore forming brines and ore deposition processes, mapping metamorphic and hydrothermal fluid provinces and pathways, and constraining the effects of fluid–rock reactions and fluid mixing.

  12. Estimation of the lake water pollution by determination of 18 elements using ICP-MS method and their statistical analysis.

    PubMed

    Komorowicz, Izabela; Gramowska, Hanka; Barałkiewicz, Danuta

    2010-01-01

    Eighteen elements (Al, As, Ba, Ca, Cd, Co, Cr, Cu, K, Li, Mg, Mn, Na, Ni, Pb, Sb, Sr and Zn) were determined in water taken from Malta Lake. All the analyses were made using the inductively coupled plasma mass spectrometry method (ICP-MS). In our investigations we focused on the variability of the element content in water from a number of sampling stations and over different seasons. The obtained results were submitted to statistical analysis. First, the results were interpreted using the analysis of variance test (ANOVA). This has revealed differences in concentration for the majority of elements with regard to seasons. Then, cluster analysis (CA) and factor analysis (FA) were applied to explore similarities between sampling stations. Neither of these have demonstrated any grouping. Finally, factor analysis and principal component analysis (PCA), applied to show the grouping of elements, revealed how different sampling stations are related to each other. PMID:20390876

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

    PubMed

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

    2001-10-20

    Nuclear weapons tests conducted by the United States in the Marshall Islands produced significant quantities of regional or tropospheric fallout contamination. Here we report on some preliminary inductively coupled plasma-mass spectrometry (ICP-MS) measurements of plutonium isolated from seven composite soil samples collected from Bikini, Enewetak and Rongelap Atolls in the northern Marshall Islands. These data show that 240Pu/239Pu isotopic signatures in surface soils from the Marshall Island vary significantly and could potentially be used to help quantify the range and extent of fallout deposition (and associated impacts) from specific weapons tests. 137Cs and 60Co were also determined on the same set of soil samples for comparative purposes. PMID:11669263

  14. 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.

  15. Determination of Sb(III) and Sb(V) by HPLC-Online isotopic dilution-ICP MS.

    PubMed

    Fontanella, Maria Chiara; Beone, Gian Maria

    2016-01-01

    This work provides a method with application of valid techniques to extract and determinate inorganic species of antimony (Sb) for water. The procedure involves•the simultaneous accumulation of Sb(III) and Sb(V) on passive samplers like Diffusive Gradient in Thin Films (DGT) with iron (Fe) oxide gel, eliminating the risk of speciation changes due to transport and storage;•application of less concentrated acid (50 mM Na2EDTA) for elution and preservation of Sb species from DGT resin;•subsequent analytical determination of inorganic species with High Performance Liquid Chromatography-Isotopic Dilution-Inductively Coupled Plasma Mass Spectrometer (HPLC-ID-ICP MS) based on determination of the isotope ratio ((123)Sb/(121)Sb) of isotopes in the samples after spiking with 123Sb enriched standard solution, reducing the effect of signal drift and matrix effect on the final value. PMID:27408828

  16. Determination of toxic metals by ICP-MS in Asiatic and European medicinal plants and dietary supplements.

    PubMed

    Filipiak-Szok, Anna; Kurzawa, Marzanna; Szłyk, Edward

    2015-04-01

    The potentially toxic metals content was determined in selected plants, used in Traditional Chinese Medicine (Angelica sinensis, Bacopa monnieri, Bupleurum sinensis, Curcuma longa, Cola accuminata, Emblica officinalis, Garcinia cambogia, Mucuna pruriens, Ocimum sanctum, Panax ginseng, Pueraria lobata, Salvia miltiorrhiza, Schisandra sinensis, Scutellaria baicalensis, Siraitia grosvenorii, Terminalia arjuna and Terminalia chebula), and some European herbs (Echinacea purpurea, Hypericum perforatum, Vitis vinifera). Samples were mineralized in a closed microwave system using HNO3 and the concentrations of Cd, Pb, Al, As, Ba, Ni and Sb were determined by ICP-MS method. Some relevant aspects of potential toxicity of metallic elements and their compounds were also discussed. Results of metal content analysis in dietary supplements available on Polish market, containing studied plants, are presented as well. The results were analyzed by principal component analysis (PCA) and cluster analysis. PMID:25467854

  17. [Determination of trace element silver in animal serum, tissues and organs by microwave digestion-ICP-MS].

    PubMed

    Yuan, Jun-Jie; Xie, You-Zhuan; Han, Chen; Sun, Wei; Zhang, Kai; Zhao, Jie; Lu, Xiao; Lu, Jian-Xi; Ren, Wei

    2014-09-01

    Nowadays, the silver is widely used in the biological field and its biological safety catches great attention. It is important to know the distribution of silver ions within the biological organism and the toxic threshold concentration in the tissue. Therefore, a highly sensitive method for measurement of trace amount of silver ion in the medical biological samples is needed. With its high sensitivity for detection of metal ions, inductively coupled plasma mass spectrometry (ICP-MS) method is well suited for quantification of trace amount of silver ion in such samples, but method development is still in its infancy. Consequently, a simple and convenient method for determination of trace amount of silver in the animal serum, tissues or organs was developed, in which the samples were subjected to the microwave digestion, followed by the ICP-MS analysis. To begin with, the samples of serum, muscle, bone marrow, bone, heart, liver, spleen, and kidney were sequently processed in 5 mL of HNO3 and 2 mL of H2O2 solution. Then the samples were completely digested by microwave with the power of 2 000 watts. The temperature was raised gradually by 3-step program. Moreover, the data achieved were reproducible and the method was time saving and especially for large amounts of sample processing. Then the digested solutions were diluted to constant volume. Finally, the concentration of 107Ag in the samples was analyzed by the method of ICP-MS under the optimized conditions. Element yttrium (Y) was used as the internal standard to compensate for matrix suppression effect and improve the accuracy of measurement. For one thing, the analytical results showed that the detection limit of the trace element 107Ag was 0.98 μg · kg(-1), and furthermore, the correlation coefficient of standard curve was 0.999 9. For another thing, the recovery rate of the silver element ranged from 98% to 107%, which was calculated according to measured quantity before adding standard, adding standard and

  18. Speciation analysis of selenium in plankton, Brazil nut and human urine samples by HPLC-ICP-MS.

    PubMed

    da Silva, Elidiane Gomes; Mataveli, Lidiane Raquel Verola; Arruda, Marco Aurélio Zezzi

    2013-06-15

    The HPLC (anion exchange)-ICP-MS technique was used for the identification (based on retention time of standards) and determination of four selenium species (selenite, selenate, selenomethionine and selenocystine) in plankton (BCR-414), Brazil nuts and urine samples. A recovery of 91% was attained for certified reference materials (BCR-414). Se(IV) was the predominant species in plankton, with the highest selenium concentration in the extract. The Brazil nuts showed only the organic species selenomethionine and selenocystine after water extraction, but after simulated gastrointestinal digestion, only selenomethionine was found as bioaccessible, corresponding to 74% of the total selenium (54.8±4.6 μg g(-1)). Analyses of the urine samples suggested the presence of selenocystine, and significant differences were observed between samples from men and women in terms of the concentration of this species after consumption of Brazil nuts (1 nut per day during 15 days).

  19. Determination of toxic metals by ICP-MS in Asiatic and European medicinal plants and dietary supplements.

    PubMed

    Filipiak-Szok, Anna; Kurzawa, Marzanna; Szłyk, Edward

    2015-04-01

    The potentially toxic metals content was determined in selected plants, used in Traditional Chinese Medicine (Angelica sinensis, Bacopa monnieri, Bupleurum sinensis, Curcuma longa, Cola accuminata, Emblica officinalis, Garcinia cambogia, Mucuna pruriens, Ocimum sanctum, Panax ginseng, Pueraria lobata, Salvia miltiorrhiza, Schisandra sinensis, Scutellaria baicalensis, Siraitia grosvenorii, Terminalia arjuna and Terminalia chebula), and some European herbs (Echinacea purpurea, Hypericum perforatum, Vitis vinifera). Samples were mineralized in a closed microwave system using HNO3 and the concentrations of Cd, Pb, Al, As, Ba, Ni and Sb were determined by ICP-MS method. Some relevant aspects of potential toxicity of metallic elements and their compounds were also discussed. Results of metal content analysis in dietary supplements available on Polish market, containing studied plants, are presented as well. The results were analyzed by principal component analysis (PCA) and cluster analysis.

  20. Comparative determination of methyl mercury in whole blood samples using GC-ICP-MS and GC-MS techniques.

    PubMed

    Hippler, J; Hoppe, H W; Mosel, F; Rettenmeier, A W; Hirner, A V

    2009-08-15

    Two methods for the determination of methyl mercury (MeHg) in whole blood samples based on different mass spectrometric detection techniques are compared. The methods were employed in two studies in which the internal exposure of a group of mercury-exposed workers to total mercury and MeHg was investigated. Blood samples of these workers were analysed for MeHg independently from each other in two laboratories using similar extraction procedures but different detection techniques, viz. coupled GC-EI-MS/ICP-MS and GC-MS using D(3)-MeHg as internal standard. MeHg was detected in all blood samples in concentrations ranging from 0.3 to 9.0 microg/L. Though different detection techniques were employed, the results obtained by the two laboratories were in relatively good agreement.

  1. [Regional effect research of blood lead concentrations and isotopic fingerprints in four cities by ICP-MS].

    PubMed

    Zeng, Jing; Wang, Jing-Yu; Liu, Ya-Qiong; Xie, Qing; Ouyang, Li

    2011-11-01

    Blood lead is a reflection of environment lead in vivo, its concentration could be used to assess lead exposure of environment quantitatively, and its isotopic ratio could be used to fingerprint environment source qualitatively. In the present study, concentrations and isotopic ratios of blood lead (BPb) of four cities in China were measured by ICP-MS for the first time. The regional effects of BPb in four Chinese cities were observed in our study. The BPb levels of industrial cities (Taiyuan and Chengdu) are higher than that of non-industrial cities (Suzhou and Beijing), indicating that industrial pollution remains primary lead contamination factor. The BPb isotopic ratios are diverse with the different character of environment the individuals live in. Food-borne lead probably has replaced the air-borne lead to be the major source of BPb in Beijing. Besides, regional effect of BPb in some developed cities is partly weakened by diversity of vast majority of imported resources.

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

    PubMed Central

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

    2016-01-01

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

  3. Determination of heavy metals in crayfish by ICP-MS with a microwave-assisted digestion treatment.

    PubMed

    López, F J Sánchez; Garcia, M D Gil; Morito, N P Sánchez; Vidal, J L Martínez

    2003-02-01

    Contamination of the American red crayfish, from the Guadiamar riverside, is due to the disastrous toxic spill that occurred on 25 April 1998 in the mining area of Aznalcóllar-Los Frailes, Spain. A high concentration of heavy metals in the waters from the mine pool and their spill to the river Guadiamar was the cause of the destruction of a great number of animal and vegetable organisms. An ICP-MS method for the total determination of heavy metals (Cu, Zn, Pb, and Cd) in whole bodies of American red crayfish (Procambarus clarkii) was used. Metals were extracted from the matrix in a closed-vessel microwave digestion system with nitric acid and hydrogen peroxide. A study of the uncertainty of the method for the determination of metals was carried out; at a concentration of 5 microg/L, the uncertainty was below 34%. PMID:12550101

  4. Determination of toxic elements in coal by ICP-MS after digestion using microwave-induced combustion.

    PubMed

    Antes, Fabiane G; Duarte, Fábio A; Mesko, Márcia F; Nunes, Matheus A G; Pereira, Vanda A; Müller, Edson I; Dressler, Valderi L; Flores, Erico M M

    2010-12-15

    A microwave-induced combustion (MIC) procedure was applied for coal digestion for subsequent determination of As, Cd and Pb by inductively coupled plasma mass spectrometry (ICP-MS) and Hg using cold vapor (CV) generation coupled to ICP-MS. Pellets of coal (500 mg) were combusted using 20 bar of oxygen and ammonium nitrate as aid for ignition. The use of nitric acid as absorbing solution (1.7, 3.5, 5.0, 7.0 and 14 mol L(-1)) was evaluated. For coal samples with higher ash content, better results were found using 7.0 mol L(-1) HNO(3) and an additional reflux step of 5 min after combustion step. For coal samples with ash content lower than 8%, 5.0 mol L(-1) nitric acid was suitable to the absorption of all analytes. Accuracy was evaluated using certified reference material (CRM) of coal and spikes. Agreement with certified values and recoveries was better than 95 and 97%, respectively, for all the analytes. For comparison of results, a procedure recommended by the American Society of Testing and Materials (ASTM) was used. Additionally, a conventional microwave-assisted digestion (MAD) in pressurized vessels was also performed. Using ASTM procedure, analyte losses were observed and a relatively long time was necessary for digestion (>6h). By comparison with MAD procedure, higher sample mass can be digested using MIC allowing better limits of detection. Additionally, the use of concentrated acids was not necessary that is an important aspect in order to obtain low blank levels and lower limits of detection, respectively. The residual carbon content in digests obtained by MAD and MIC was about 15% and <1%, respectively, showing the better digestion efficiency of MIC procedure. Using MIC it was possible to digest completely and simultaneously up to eight samples in only 25 min with relatively lower generation of laboratory effluents. PMID:21111147

  5. A simple method for rapid, high-precision isotope measurements of small samples with MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Kamenov, G. D.; Mueller, P. A.; Gilli, A.; Coyner, S. J.; Nielsen, S. H.

    2006-12-01

    A key factor for accurate and precise isotopic measurements is optimal signal to noise ratio, which makes analyses of very small samples challenging due to the small number of available analyte ions. If, however, the analysis time can be drastically reduced, then very small samples (e.g., 1ng) can be analyzed by placing the analyte ions in small volumes (e.g., 0.1ml). This will result in 10ppb sample solution and will give acceptable signal to noise ratio on Faraday detectors on modern MC-ICP-MS instruments. The signal from a 0.1ml solution, however, will last no more than a minute and very few ratios will be acquired with traditional isotope measurement protocols. In a series of experiments with standard reference materials and samples we established that high-precision isotopic ratio measurements can be obtained in much shorter times compared to traditional methods for isotopic analyses using TIMS and MC-ICP-MS. The protocol utilizes the Nu Plasma TRA (time-resolved analysis) software operating with a 0.2 second acquisition time (i.e., 300 isotopic ratios/minute). Using a low- flow nebulizer, only 0.1-0.2 ml of sample solution is required for 1-2 minutes signal duration. Consequently, placing the available analytical ions in small volume leads to higher signal to noise ratio that results in precise isotopic analyses, regardless of the very short acquisition times employed during the experiments. This technique can be applied for analyses of virtually any isotope system, as we demonstrate with examples for Sr, Nd, and Pb isotopic measurements. In addition to high-precision isotopic analyses of very small samples on Faraday detectors, another advantage of this protocol is enhanced lab productivity because overall analysis time is significantly reduced.

  6. Determination of toxic elements in coal by ICP-MS after digestion using microwave-induced combustion.

    PubMed

    Antes, Fabiane G; Duarte, Fábio A; Mesko, Márcia F; Nunes, Matheus A G; Pereira, Vanda A; Müller, Edson I; Dressler, Valderi L; Flores, Erico M M

    2010-12-15

    A microwave-induced combustion (MIC) procedure was applied for coal digestion for subsequent determination of As, Cd and Pb by inductively coupled plasma mass spectrometry (ICP-MS) and Hg using cold vapor (CV) generation coupled to ICP-MS. Pellets of coal (500 mg) were combusted using 20 bar of oxygen and ammonium nitrate as aid for ignition. The use of nitric acid as absorbing solution (1.7, 3.5, 5.0, 7.0 and 14 mol L(-1)) was evaluated. For coal samples with higher ash content, better results were found using 7.0 mol L(-1) HNO(3) and an additional reflux step of 5 min after combustion step. For coal samples with ash content lower than 8%, 5.0 mol L(-1) nitric acid was suitable to the absorption of all analytes. Accuracy was evaluated using certified reference material (CRM) of coal and spikes. Agreement with certified values and recoveries was better than 95 and 97%, respectively, for all the analytes. For comparison of results, a procedure recommended by the American Society of Testing and Materials (ASTM) was used. Additionally, a conventional microwave-assisted digestion (MAD) in pressurized vessels was also performed. Using ASTM procedure, analyte losses were observed and a relatively long time was necessary for digestion (>6h). By comparison with MAD procedure, higher sample mass can be digested using MIC allowing better limits of detection. Additionally, the use of concentrated acids was not necessary that is an important aspect in order to obtain low blank levels and lower limits of detection, respectively. The residual carbon content in digests obtained by MAD and MIC was about 15% and <1%, respectively, showing the better digestion efficiency of MIC procedure. Using MIC it was possible to digest completely and simultaneously up to eight samples in only 25 min with relatively lower generation of laboratory effluents.

  7. Multielement analysis of micro-volume biological samples by ICP-MS with highly efficient sample introduction system.

    PubMed

    Takasaki, Yuka; Inagaki, Kazumi; Sabarudin, Akhmad; Fujii, Shin-Ichiro; Iwahata, Daigo; Takatsu, Akiko; Chiba, Koichi; Umemura, Tomonari

    2011-12-15

    A method for multielement analysis of micro-volume biological sample by inductively coupled plasma mass spectrometry (ICP-MS) with a highly efficient sample introduction system was presented. The sample introduction system was the combination of (1) an inert loop injection unit and (2) a high performance concentric nebulizer (HPCN) coupled with a temperature controllable cyclone chamber. The loop injection unit could introduce 20 μL samples into the carrier liquid flow of 10 μL min(-1) producing a stable signal for 100s without any dilution. The injection loop is continuously washed with 0.1M HNO(3) carrier solution during the measurement, thereby much improving sample throughput. The HPCN is a triple tube concentric nebulizer, which can generate fine aerosols and provide a stable and highly measurement sensitivity in ICP-MS at a liquid flow rate less than 10 μL min(-1). With the combination of the chamber heating at 60°C, the sensitivity obtained with the proposed sample introduction system at the liquid flow rate of 10 μL min(-1) was almost the same as that with a common concentric nebulizer and cyclone chamber system at the liquid flow rate of 1 mL min(-1), though the sample consumption rate of the HPCN was two orders of the magnitude lower than that of the common nebulizer. The validation of the proposed system was performed by analyzing the NIST SRM 1577b Bovine Liver. The observed values for 12 elements such as Na, P, S, K, Ca, Mn, Fe, Co, Cu, Zn, Mo, Cd were in good agreement with their certified values and information value. Satisfactory analytical results for 14 elements such as Na, Mg, P, S, K, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Y, Ba in Escherichia coli sample were also obtained. The proposed sample introduction system was quite effective in the cases when only micro-volume of biological sample is available. PMID:22099643

  8. [Determination of inorganic elements in rat serum, and vegetable and fruit ferment liquid by ICP-MS].

    PubMed

    Li, Xiang-yun; Lian, Hong-zhen; Chen, Yi-jun; Hu, Xin; Mao, Li; Lu, Ming; Cai, Yun-qing

    2008-09-01

    In the present paper, the contents of thirteen inorganic elements in rat serum, and vegetable and fruit ferment liquid (VFFL) were measured by ICP-MS in order to study the anti-tumor effect of VFFL. Serum or VFFL was digested in nitric and perchloric acids at room temperature and then heated until dryness. The residue was dissolved with 1% (phi) nitric acid prior to ICP-MS analysis. The element contents were quantitated by using 45Sc, 103Rh and 187Re as the internal standards, respectively, according to the rule of close mass number. Certificate references bovine serum (GBW(E)090006) and tea (GBW070605) were employed to validate the proposed method, and the analysis results of most elements in two certificate references were in agreement with their reference values. The intra-day and inter-day precisions of the method in terms of relative standard deviation (RSD) were mainly below 10% and below 15%, respectively. The spiked recoveries for most of studied elements were 80%-110% in rat serum and 90%-120% in VFFL. This method was rapid, highly sensitive, and especially suitable to being applied to small quantity of biological samples with greatly different elements contents. Therefore, we measured the content of thirteen elements in the sera of rats, where in were induced liver cancer by revulsant, and the rate were fed with different dosage of VFFL in intragastric infusion at the same time. It was preliminarily found that the concentrations of some elements in sera of different experiment groups of rats were significantly different, implying the potential anti-tumor effects of VFFL. PMID:19093589

  9. History of individuals of the 18th/19th centuries stored in bones, teeth, and hair analyzed by LA-ICP-MS--a step in attempts to confirm the authenticity of Mozart's skull.

    PubMed

    Stadlbauer, Christina; Reiter, Christian; Patzak, Beatrix; Stingeder, Gerhard; Prohaska, Thomas

    2007-06-01

    A cranium stored in the Stiftung Mozarteum in Salzburg/Austria which is believed to be that of Mozart, and skeletal remains of suspected relatives which have been excavated from the Mozart family grave in the cemetery in Salzburg, have been subjected to scientific investigations to determine whether or not the skull is authentic. A film project by the Austrian television ORF in collaboration with Interspot Film on this issue was broadcast at the beginning of the "Mozart year 2006". DNA analysis could not clarify relationships among the remains and, therefore, assignment of the samples was not really possible. In our work this skull and excavated skeletal remains have been quantified for Pb, Cr, Hg, As, and Sb content by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to obtain information about the living conditions of these individuals. A small splinter of enamel (less than 1 mm(3)) from a tooth of the "Mozart cranium" was also available for investigation. Quantification was performed by using spiked hydroxyapatite standards. Single hair samples which are recorded to originate from Mozart have also been investigated by LA-ICP-MS and compared with hair samples of contemporary citizens stored in the Federal Pathologic-Anatomical Museum, Vienna. In general, Pb concentrations up to approximately 16 mug g(-1) were found in the bone samples of 18th century individuals (a factor of 7 to 8 higher than in recent samples) reflecting elevated Pb levels in food or beverages. Elevated Pb levels were also found in hair samples. The amount of Sb in the enamel sample of the "Mozart cranium" (approx. 3 mug g(-1)) was significantly higher than in all the other tooth samples investigated, indicating possible Sb ingestion in early childhood. Elevated concentrations of elements in single hair samples gave additional information about possible exposure of the individuals to heavy metals at a particular point in their life.

  10. Late Neoproterozoic magmatism in South Qinling, Central China: Geochemistry, zircon U-Pb-Lu-Hf isotopes and tectonic implications

    NASA Astrophysics Data System (ADS)

    Wang, Ruirui; Xu, Zhiqin; Santosh, M.; Yao, Yuan; Gao, Li'e.; Liu, Chunhua

    2016-06-01

    The Neoproterozoic tectonic evolution of the northern margin of the Yangtze Block in South China remains debated. In this study, we present results from LA-ICP-MS zircon U-Pb geochronology on a suite of intermediate-felsic rocks in South Qinling, Central China which show a mean age of ca. 630 Ma. The zircon εHf(t) values of these rocks mostly range from + 0.44 to + 14.78. Geochemically, the granites and syenite show high total alkali contents, with enrichment in LREE, LILE (Rb, Ba, and K), and HFSE (Th, U, Nb, Ta, Zr, and Hf), and depletion in Sr, P, and Ti, similar to the features of A-type granites. The meta-diorite shows high Na2O, with depletion in Eu, Ti, and LILE (Sr, Rb, Ba, and K), and enrichment in HFSE (Th, U, Nb, Ta, Zr, and Hf). The geochemical features are consistent with formation of the intermediate-felsic suite through fractionation from underplated basaltic magma that originated from sub-continental lithospheric mantle metasomatized by asthenosphere-derived oceanic-island-basalt-like (OIB-like) melts, coupled with minor crustal contamination. We correlate the ca. 630 Ma magmatism with a back-arc rift setting that probably developed in relation to slab tearing during continued slab rollback.

  11. Detrital zircon U-Pb ages of Paleozoic sedimentary rocks from the eastern Hexi Corridor Belt (NW China): Provenance and geodynamic implications

    NASA Astrophysics Data System (ADS)

    Zhao, Xiaochen; Liu, Chiyang; Wang, Jianqiang; Zhao, Yan; Wang, Lei; Zhang, Qihang

    2016-06-01

    The Paleozoic tectonic framework of the eastern Hexi Corridor Belt is ambiguous. However, thick Paleozoic sediments from the eastern Hexi Corridor Belt can provide clues to this problem. In this paper, we deal with the detrital zircon provenance of Middle Ordovician to Late Devonian strata using LA-ICP-MS U-Pb dating, documenting the temporal and spatial changes of provenance. Detrital zircon U-Pb ages indicate that the primary provenance was the Qilian Orogenic Belt and the Alxa Block. However, two samples from Late Devonian strata show different provenance characteristics, from the North Qilian Orogenic Belt, and the Alxa Block and the North China Block, respectively. Different age distributions through time reflect provenance changes due to continuous convergence of the Central Qilian Block and the Alxa Block from the Middle Ordovician to Late Devonian. A significant age cluster ranging from 2000 to 1800 Ma, which is a detrital zircon signature of the North China Block, appeared in the Late Devonian Zhongning Formation. Our preferred interpretation is that the amalgamation of the Alxa Block and the North China Block likely occurred at that time. Moreover, similar Paleozoic fossils, paleolatitudes and detrital zircon distribution indicate that the Hexi Corridor Belt has an affinity to eastern Gondwana.

  12. Novel calibration for LA-ICP-MS-based fission-track thermochronology

    NASA Astrophysics Data System (ADS)

    Soares, C. J.; Guedes, S.; Hadler, J. C.; Mertz-Kraus, R.; Zack, T.; Iunes, P. J.

    2014-01-01

    We present a novel age-equation calibration for fission-track age determinations by laser ablation inductively coupled plasma mass spectrometry. This new calibration incorporates the efficiency factor of an internal surface, [ ηq]is, which is obtained by measuring the projected fission-track length, allowing the determination of FT ages directly using the recommended spontaneous fission decay constant. Also, the uranium concentrations in apatite samples are determined using a Durango (Dur-2, 7.44 μg/g U) crystal and a Mud Tank (MT-7, 6.88 μg/g U) crystal as uranium reference materials. The use of matrix-matched reference materials allows a reduction in the uncertainty of the uranium measurements to those related to counting statistics, which are ca. 1 % taking into account that no extra source of uncertainty has to be considered. The equations as well as the matrix-matched reference materials are evaluated using well-dated samples from Durango, Fish Canyon Tuff, and Limberg as unknown samples. The results compare well with their respective published ages determined through other dating methods. Additionally, the results agree with traditional fission-track ages using both the zeta approach and the absolute approach, suggesting that the calibration presented in this work can be robustly applied in geological context. Furthermore, considering that fission-track ages can be determined without an age standard sample, the fission-track thermochronology approach presented here is assumed to be a valuable dating tool.

  13. Disturbed Sr and Nd Isotope Systematics in Zircons With Concordant SHRIMP U-Pb Ages

    NASA Astrophysics Data System (ADS)

    Weaver, K. L.; Bennett, V. C.; Depaolo, D. J.; Mundil, R.

    2004-12-01

    Little is known about the Sr- and Nd-isotopic systematics of zircon. With slow diffusion rates and a high resistance to weathering, zircon should preserve accurate age information and initial Sr and Nd isotopic ratios. As a common accessory mineral, it could provide petrogenetic information for rocks that have been altered, weathered, or metamorphosed. We have investigated the Sm-Nd and Rb-Sr systematics of zircons from unmetamorphosed granitic rocks that have yielded concordant U-Pb SHRIMP (Sensitive High Resolution Ion Microprobe) ages and have depleted mantle signatures for Nd and Sr isotopes. Zircon populations from mantle-derived igneous rocks with ages of 0.1, 1.7, and 3.8 Ga were chosen for Sr and Nd isotopic analysis. Low concentrations (Sr, 4 to 8 ppm and Nd, 6 to 12 ppm) and small grain size necessitate the use of multigrain aliquots. Meaningful results can be obtained only if all of the zircons in the rock are a coherent population with homogeneous ages throughout and among grains. Zircon U-Pb ages were characterized using the SHRIMP RG, and trace element concentrations were measured by LA-ICPMS. The populations are homogeneous and the material ablated by the ion beam ( ˜~20 μ m spot size) shows little evidence of lead loss. Results on zircons of 100 Ma and 1700 Ma indicate that both the Rb-Sr and Sm-Nd systems have been severely disturbed. For the 1700 Ma granitic rocks from the Yavapai sequence of Arizona, zircon Sm-Nd apparent ages are ca. 1000 Ma! Leaching was used to remove contributions from adhering or included minerals, but leached residues that presumably most closely approximate the composition of the pure zircon (e.g. have high Sm/Nd) are no less disturbed than unleached samples. Despite the U-Pb SHRIMP ages indicating a closed system, the zircons have failed to preserve a reasonable age or initial isotopic composition for Sr and Nd, indicating that parts of the crystal might be severely affected by radiation damage resulting in disturbed

  14. Simultaneous determination of radiocesium ((135)Cs, (137)Cs) and plutonium ((239)Pu, (240)Pu) isotopes in river suspended particles by ICP-MS/MS and SF-ICP-MS.

    PubMed

    Cao, Liguo; Zheng, Jian; Tsukada, Hirofumi; Pan, Shaoming; Wang, Zhongtang; Tagami, Keiko; Uchida, Shigeo

    2016-10-01

    Due to radioisotope releases in the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident, long-term monitoring of radiocesium ((135)Cs and (137)Cs) and Pu isotopes ((239)Pu and (240)Pu) in river suspended particles is necessary to study the transport and fate of these long-lived radioisotopes in the land-ocean system. However, it is expensive and technically difficult to collect samples of suspended particles from river and ocean. Thus, simultaneous determination of multi-radionuclides remains as a challenging topic. In this study, for the first time, we report an analytical method for simultaneous determination of radiocesium and Pu isotopes in suspended particles with small sample size (1-2g). Radiocesium and Pu were sequentially pre-concentrated using ammonium molybdophosphate and ferric hydroxide co-precipitation, respectively. After the two-stage ion-exchange chromatography separation from the matrix elements, radiocesium and Pu isotopes were finally determined by ICP-MS/MS and SF-ICP-MS, respectively. The interfering elements of U ((238)U(1)H(+) and (238)U(2)H(+) for (239)Pu and (240)Pu, respectively) and Ba ((135)Ba(+) and (137)Ba(+) for (135)Cs and (137)Cs, respectively) were sufficiently removed with the decontamination factors of 1-8×10(6) and 1×10(4), respectively, with the developed method. Soil reference materials were utilized for method validation, and the obtained (135)Cs/(137)Cs and (240)Pu/(239)Pu atom ratios, and (239+240)Pu activities showed a good agreement with the certified/information values. In addition, the developed method was applied to analyze radiocesium and Pu in the suspended particles of land water samples collected from Fukushima Prefecture after the FDNPP accident. The (135)Cs/(137)Cs atom ratios (0.329-0.391) and (137)Cs activities (23.4-152Bq/g) suggested radiocesium contamination of the suspended particles mainly originated from the accident-released radioactive contaminates, while similar Pu contamination of suspended

  15. Simultaneous determination of radiocesium ((135)Cs, (137)Cs) and plutonium ((239)Pu, (240)Pu) isotopes in river suspended particles by ICP-MS/MS and SF-ICP-MS.

    PubMed

    Cao, Liguo; Zheng, Jian; Tsukada, Hirofumi; Pan, Shaoming; Wang, Zhongtang; Tagami, Keiko; Uchida, Shigeo

    2016-10-01

    Due to radioisotope releases in the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident, long-term monitoring of radiocesium ((135)Cs and (137)Cs) and Pu isotopes ((239)Pu and (240)Pu) in river suspended particles is necessary to study the transport and fate of these long-lived radioisotopes in the land-ocean system. However, it is expensive and technically difficult to collect samples of suspended particles from river and ocean. Thus, simultaneous determination of multi-radionuclides remains as a challenging topic. In this study, for the first time, we report an analytical method for simultaneous determination of radiocesium and Pu isotopes in suspended particles with small sample size (1-2g). Radiocesium and Pu were sequentially pre-concentrated using ammonium molybdophosphate and ferric hydroxide co-precipitation, respectively. After the two-stage ion-exchange chromatography separation from the matrix elements, radiocesium and Pu isotopes were finally determined by ICP-MS/MS and SF-ICP-MS, respectively. The interfering elements of U ((238)U(1)H(+) and (238)U(2)H(+) for (239)Pu and (240)Pu, respectively) and Ba ((135)Ba(+) and (137)Ba(+) for (135)Cs and (137)Cs, respectively) were sufficiently removed with the decontamination factors of 1-8×10(6) and 1×10(4), respectively, with the developed method. Soil reference materials were utilized for method validation, and the obtained (135)Cs/(137)Cs and (240)Pu/(239)Pu atom ratios, and (239+240)Pu activities showed a good agreement with the certified/information values. In addition, the developed method was applied to analyze radiocesium and Pu in the suspended particles of land water samples collected from Fukushima Prefecture after the FDNPP accident. The (135)Cs/(137)Cs atom ratios (0.329-0.391) and (137)Cs activities (23.4-152Bq/g) suggested radiocesium contamination of the suspended particles mainly originated from the accident-released radioactive contaminates, while similar Pu contamination of suspended

  16. EXTRACTION AND DETECTION OF A NEW ARSINE SULFIDE CONTAINING ARSENOSUGAR IN MOLLUSCS BY IC-ICP-MS AND IC-ESI-MS/MS

    EPA Science Inventory

    Using IC-ICP-MS and IC-ESI-MS/MS, an unknown arsenical compound in mollusks has been identified as a new arsine sulfide containing analog of a known arsenosugar and is referred to as As(498). This species has been observed in four separate shellfish species following a mild metha...

  17. Trace Elements in Ivory Coast Tektites, Microtektites, and Fallback Particles of the Lake Bosumtwi Impact Crater, Ghana: A LA-ICP-MS Study

    NASA Astrophysics Data System (ADS)

    Luetke, S.; Deutsch, A.; Berndt, J.; Langenhorst, F.

    2008-03-01

    LA-ICP-MS trace element data of Ivory Coast tektites, microtektites, and glassy fallback particles indicate a soil contribution to the precursor materials of the tektites. A variable Ni/Co ratio seems to be characteristic of the fallback particles.

  18. DETECTION AND QUANTIFICATION OF A THIO-ARSENOSUGAR IN MARINE MOLLUSKS BY IC-ICP-MS WITH AN EMPHASIS ON THE INTERACTION OF ARSENOSUGARS WITH SULFIDE

    EPA Science Inventory

    Arsenosugars can make up a significant portion of the total arsenic in shellfish. These arsenosugars can be present in their oxide or sulfide form. IC-ICP-MS and IC-ESI-MS/MS data will be presented that indicates the presence of As(328-S) and As(328) in three species of marine ...

  19. Provenance of Modern Soils and Limestone and Chert Bedrock of Middle Tennessee Assessed Using Detrital Zircon U-Pb Geochronology

    NASA Astrophysics Data System (ADS)

    Ayers, J. C.; Katsiaficas, N. J.; Wang, X.

    2014-12-01

    Relatively thick soils mantle limestone bedrock throughout much of middle TN. Detrital zircon U-Pb geochronology was used to test two hypotheses: 1) That soil formed by accumulation of insoluble residue during chemical weathering of "dirty" limestone bedrock. 2) That an exotic component, perhaps wind-blown loess, was deposited and weathered to form soil. Samples of soil and underlying bedrock were collected from flat surfaces at the tops of cliffs. At Site 1 the Mississippian cherty limestone of the Fort Payne Formation was collected along with the B1 and B2 horizons of the overlying ultisol. At Site 2 a composite sample of A and B horizons of an alfisol and a sample of the underlying Ordovician limestone of the Hermitage Formation were collected. Zircon was recovered from soil and limestone samples, imaged using cathodoluminescence, and analyzed for trace elements and U-Pb isotopes using a 193 nm laser and quadrupole ICP-MS. Discordant analyses were discarded and 206Pb/238U ages are reported. Trace element concentrations and ratios in zircon seem to not be useful as provenance indicators. However, comparison of U-Pb age spectra showed that soils at both sites predominantly formed by weathering of limestone, with a small exotic component. The Hermitage has significant age peaks at ~1330, 1043, 955 and 439 Ma, and its overlying soil has age peaks at 1410, 1235, 1036 and 442 Ma. The age spectra are significantly different (Kolmogorov-Smirnov probability P = 0.01 < 0.05 significance). The Fort Payne has age peaks at ~1253, 967 and 417 Ma, while the B1 has age peaks at 1440, 1182, 1012 and 450 Ma (K-S P = 0.051) and the B2 at 1240, 941, 362, 81 and 33 Ma (K-S P = 0.073). The young ages in B2 require an exotic component that may account for ~25% of the measured ages. The source of the exotic material has not yet been identified, but its zircon age spectrum does not match previously published age spectra for the regional Pleistocene Peoria loess. Bedrock age peaks

  20. A new approach for calibration of laser ablation inductively coupled plasma mass spectrometry using thin layers of spiked agarose gels as references.

    PubMed

    Stärk, H-J; Wennrich, Rainer

    2011-02-01

    Calibration of analytical methods using laser ablation for sample introduction is often problematic. The availability of matrix-adapted standard materials is a crucial factor in the analysis of biological samples in particular. In this work a method for preparation of thin-film references for LA-ICP-MS is presented which is inexpensive, relatively simple and generally practicable. Aqueous solutions of agarose spiked with defined amounts of the analytes were cast on a carrier and then dried. When the thin-film references were characterized the average thickness of the films was 0.03 mm in the centre of the film and the relative standard deviation was 8%. Nebulization ICP-MS analysis after acid digestion of the agarose film was used to investigate the effectiveness of the spiking procedure. Recovery of the spiked elements was frequently in the range 90-110% (for rare earth elements 97-102%). Laser ablation ICP-MS analysis was used to investigate the distribution of the spiked elements in the film. When the laser was scanned across the gel the measured intensities were not constant, but had a peak-shaped profile with a flat top. Use of this flat-top region for analytical purposes, after its characterization by laser ablation ICP-MS, is proposed. Analysis of cell cultures was carried out by direct laser ablation-ICP-MS with the calibration method described. The results were in accordance with values previously achieved by nebulization ICP-MS.

  1. Oxygen isotopic composition and U-Pb discordance in zircon

    USGS Publications Warehouse

    Booth, A.L.; Kolodny, Y.; Chamberlain, C.P.; McWilliams, M.; Schmitt, A.K.; Wooden, J.

    2005-01-01

    We have investigated U-Pb discordance and oxygen isotopic composition of zircon using high-spatial resolution ??18O measurement by ion microprobe. ??18O in both concordant and discordant zircon grains provides an indication of the relationship between fluid interaction and discordance. Our results suggest that three characteristics of zircon are interrelated: (1) U-Pb systematics and concomitant age discordance, (2) ??18O and the water-rock interactions implied therein, and (3) zircon texture, as revealed by cathodoluminescence and BSE imaging. A key observation is that U-Pb-disturbed zircons are often also variably depleted in 18O, but the relationship between discordance and ??18O is not systematic. ??18O values of discordant zircons are generally lighter but irregular in their distribution. Textural differences between zircon grains can be correlated with both U-Pb discordance and ??18O. Discordant grains exhibit either a recrystallized, fractured, or strongly zoned CL texture, and are characteristic of 18O depletion. We interpret this to be a result of metamictization, leading to destruction of the zircon lattice and an increased susceptibility to lead loss. Conversely, grains that are concordant have less-expressed zoning and a smoother CL texture and are enriched in 18O. From this it is apparent that various stages of water-rock interaction, as evidenced by systematic variations in ??18O, leave their imprint on both the texture and U-Pb systematics of zircon. Copyright ?? 2005 Elsevier Ltd.

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

    PubMed

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

    2013-11-01

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

  3. Metal and metalloid multi-elementary ICP-MS validation in whole blood, plasma, urine and hair. Reference values.

    PubMed

    Goullé, Jean-Pierre; Mahieu, Loïc; Castermant, Julien; Neveu, Nicolas; Bonneau, Laurent; Lainé, Gilbert; Bouige, Daniel; Lacroix, Christian

    2005-10-01

    Four multi-elementary metal and metalloid quantification methods using inductively coupled plasma mass spectrometry (ICP-MS) were developed and validated in human whole blood, plasma, urine and hair by means of a single preparation procedure for each sample. The ICP-MS measurements were performed using a Thermo Elemental X7CCT series and PlasmaLab software without a dynamic reaction cell. With this procedure 27-32 elements can be simultaneously quantified in biological matrices: Li, Be, B, Al, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Mo, Pd, Ag, Cd, Sn, Sb, Te, Ba, W, Pt, Hg, Tl, Pb, Bi, U. Whole blood, plasma and urine samples (0.4 ml each) were diluted with purified water, acid, triton X100 and butanol. Rhodium was used as internal standard. The urine sample results were corrected for enzymatic creatinine determination. Twenty-five milligrams hair samples were acid mineralized after a decontamination procedure and diluted as previously described for biological fluids. To be validated, each element had to show linearity with a correlation coefficient higher than 0.99. The intra-assay and inter-assay inaccuracy, measured as the variation coefficient, were below 5 and 10% respectively. Global performance was assessed by a quality control program. Our laboratory is a registered participant of the Institut National de Santé Publique du Québec (Sainte-Foy, Canada) inter-laboratory comparison program for whole blood, urine, and beard hair of non-occupationally exposed individuals spiked with selected elements. In our study multi-element metal and metalloid analysis was assessed for 27 elements in whole blood, 27 elements in plasma, 30 elements in urine and 32 elements in hair, from 0 to 25, or 250 to 1000 ng/ml, depending on the element. Quantification limits ranged from 0.002 ng/ml (U) to 8.1 ng/ml (Al) for whole blood, from 0.002 ng/ml (U) to 7.7 ng/ml (Al) for plasma, from 0.001 ng/ml (U) to 2.2 ng/ml (Se) for urine, and from 0.2 pg/mg (Tl) to 0.5 ng

  4. Single particle ICP-MS as a tool for determining the stability of silver nanoparticles in aquatic matrixes under various environmental conditions, including treatment by ozonation.

    PubMed

    Telgmann, Lena; Nguyen, Michael Thanh Khoa; Shen, Li; Yargeau, Viviane; Hintelmann, Holger; Metcalfe, Chris D

    2016-07-01

    Silver nanoparticles (AgNPs) are used in a large number of consumer products due to their antimicrobial and antifungal properties, and these materials may be discharged into municipal wastewater. Wastewater treatment, including advanced oxidation processes (AOPs), may modify the forms of silver in wastewater before they are discharged into surface waters. In addition, little is known about the changes in AgNPs that occur in natural waters under different environmental conditions. In this project, we utilized single particle ICP-MS (spICP-MS) and dynamic light scattering (DLS) analytical techniques to evaluate changes in the number and size of AgNPs in laboratory experiments with milliQ water under different environmental conditions, as well as during ozonation. Changes in the number and size of AgNPs determined by spICP-MS were evidence of altered stability of the nanoparticles. Increased rates of dissolution occurred under extremes of pH. Lower temperature decreased the rate of dissolution of AgNP relative to the dissolution in treatments at room temperature. The addition of chloride resulted in the loss of AgNPs from suspension due to agglomeration and precipitation. Ozonation led to a rapid decline in the number and size of AgNPs, as indicated by both spICP-MS and DLS analysis. An increase in the concentration of dissolved silver in the ozone treatments was evidence that changes in particle size were a result of oxidative dissolution of AgNPs to silver ion. Graphical abstract Single particle ICP-MS is used to evaluate dissolution of silver nanoparticles under different environmental conditions, including water treatment by ozonation.

  5. Single particle ICP-MS as a tool for determining the stability of silver nanoparticles in aquatic matrixes under various environmental conditions, including treatment by ozonation.

    PubMed

    Telgmann, Lena; Nguyen, Michael Thanh Khoa; Shen, Li; Yargeau, Viviane; Hintelmann, Holger; Metcalfe, Chris D

    2016-07-01

    Silver nanoparticles (AgNPs) are used in a large number of consumer products due to their antimicrobial and antifungal properties, and these materials may be discharged into municipal wastewater. Wastewater treatment, including advanced oxidation processes (AOPs), may modify the forms of silver in wastewater before they are discharged into surface waters. In addition, little is known about the changes in AgNPs that occur in natural waters under different environmental conditions. In this project, we utilized single particle ICP-MS (spICP-MS) and dynamic light scattering (DLS) analytical techniques to evaluate changes in the number and size of AgNPs in laboratory experiments with milliQ water under different environmental conditions, as well as during ozonation. Changes in the number and size of AgNPs determined by spICP-MS were evidence of altered stability of the nanoparticles. Increased rates of dissolution occurred under extremes of pH. Lower temperature decreased the rate of dissolution of AgNP relative to the dissolution in treatments at room temperature. The addition of chloride resulted in the loss of AgNPs from suspension due to agglomeration and precipitation. Ozonation led to a rapid decline in the number and size of AgNPs, as indicated by both spICP-MS and DLS analysis. An increase in the concentration of dissolved silver in the ozone treatments was evidence that changes in particle size were a result of oxidative dissolution of AgNPs to silver ion. Graphical abstract Single particle ICP-MS is used to evaluate dissolution of silver nanoparticles under different environmental conditions, including water treatment by ozonation. PMID:27311958

  6. U-Pb zircon and CHIME monazite dating of granitoids and high-grade metamorphic rocks from the Eastern and Peninsular Thailand - A new report of Early Paleozoic granite

    NASA Astrophysics Data System (ADS)

    Kawakami, T.; Nakano, N.; Higashino, F.; Hokada, T.; Osanai, Y.; Yuhara, M.; Charusiri, P.; Kamikubo, H.; Yonemura, K.; Hirata, T.

    2014-07-01

    In order to understand the age and tectonic framework of Eastern to Peninsular Thailand from the viewpoint of basement (metamorphic and plutonic) geology, the LA-ICP-MS U-Pb zircon dating and the chemical Th-U-total Pb isochron method (CHIME) monazite dating were performed in the Khao Chao, Hub-Kapong to Pran Buri, and Khanom areas in Eastern to Peninsular Thailand. The LA-ICP-MS U-Pb zircon dating of the garnet-hornblende gneiss from the Khao Chao area gave 229 ± 3 Ma representing the crystallization age of the gabbro, and that of the garnet-biotite gneisses gave 193 ± 4 Ma representing the timing of an upper amphibolite facies metamorphism. The CHIME monazite dating of pelitic gneiss from the Khao Chao gneiss gave scattered result of 68 ± 22 Ma, due to low PbO content and rejuvenation of older monazite grains during another metamorphism in the Late Cretaceous to Tertiary time. The U-Pb ages of zircon from the Hua Hin gneissic granite in the Hub-Kapong to Pran Buri area scatter from 250 Ma to 170 Ma on the concordia. Granite crystallization was at 219 ± 2 Ma, followed by the sillimanite-grade regional metamorphism at 185 ± 2 Ma. Monazite in the pelitic gneiss from this area also preserves Early to Middle Jurassic metamorphism and rejuvenation by later contact metamorphism by non-foliated granite or by another fluid infiltration event in the Late Cretaceous to Tertiary time. The Khao Dat Fa granite from the Khanom area of Peninsular Thailand gave a U-Pb zircon age of 477 ± 7 Ma. This is the second oldest granite pluton ever reported from Thailand, and is a clear evidence for the Sibumasu block having a crystalline basement that was formed during the Pan-African Orogeny. The Khao Pret granite gives U-Pb zircon concordia age of 67.5 ± 1.3 Ma, which represents the timing of zircon crystallization from the granitic melt and accompanied sillimanite-grade contact metamorphism against surrounding metapelites and gneisses. Metamorphic rocks in the Doi Inthanon area

  7. The role of U-Pb ages of detrital zircons in sedimentology-An alarming case study for the impact of sampling for provenance interpretation

    NASA Astrophysics Data System (ADS)

    Zimmermann, Udo; Andersen, Tom; Madland, Merete Vadla; Larsen, Ingrid Skipenes

    2015-05-01

    U-Pb ages on detrital zircons are often utilised for stratigraphic and paleogeographic interpretations and correlation. Sampling is carried out in such a way that the samples are representative for a formation, and then used for provenance identification and/or defining a maximum time limit for deposition. Is it possible that sedimentological factors and sampling would influence the results? This is perhaps an obvious consideration for sedimentologists, but is in many studies treated as a secondary concern or even not mentioned. U-Pb LA-ICP-MS analysis on detrital zircons from two samples of Cambrian age (Herrería Formation, Cantabrian Mountains, Spain) revealed very different provenance signatures at the base and top of the formation. Both successions have been deposited in a shallow marine environment, are lithologically comparable (arenites, feldspathic arenites, siltstone, shales intercalated with marls and dolomite) and differ only slightly in age. Nearly 80% of all detrital zircons (n = 152; discordance ≤ 10) at the base of the formation are younger than 650 Ma. Detrital zircons older than 1.0 Ga amount to only 10% (n = 16) of the entire population. In contrast, only around 32% of all detrital zircons from the top of the formation (n = 123; discordance ≤ 10) are younger than 650 Ma while more than 16% are Archean and nearly 50% Paleoproterozoic. This implies a fundamental change in provenance, with a shift from Neoproterozoic to Paleoproterozoic (1.9-2.2 Ga) aged sediment sources. Consequently, changes of sediment transport systems have had an extremely profound impact on the provenance of the formation. Therefore, when correlating sedimentary rocks, interpreting source rocks and modelling paleogeography from U-Pb ages of detrital zircons, sedimentological parameters are possibly paramount and these need to be at least discussed before any interpretation is made.

  8. Iron isotopes in natural carbonate minerals determined by MC-ICP-MS with a 58Fe- 54Fe double spike

    NASA Astrophysics Data System (ADS)

    Dideriksen, K.; Baker, J. A.; Stipp, S. L. S.

    2006-01-01

    We have developed a method for iron isotope analysis by multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) using a 58Fe- 54Fe double spike. A 20 min analysis produces mass-bias-corrected iron isotope data with an external reproducibility of ±0.05 (2 SD) on δ56Fe, which represents a decrease in analysis time compared to sample-standard bracketing techniques. The estimation of external reproducibility is based on replicate analysis of the ETH hematite in-house standard. The double spike method has two advantages. First, matrix effects during MC-ICP-MS analysis are decreased with tests showing that accurate iron isotope data can, in some cases, be obtained even when matrix levels exceed iron concentration (Na/Fe, Mg/Fe, and Ca/Fe up to 5, 2, and 0.1, respectively). Because chemical separation reduces matrix/Fe to levels more than three orders of magnitude lower than this, measured Fe isotope compositions are unlikely to be compromised by matrix effects. Second, it is possible to spike samples before chemical purification, which enables any isotopic fractionation effect because of incomplete recovery of iron from a sample to be accounted for. This may be important where obtaining quantitative iron yields from samples is difficult, such as the extraction of dissolved iron from water samples. Fe isotope data on a set of standard reference materials (igneous rocks, ferromanganese nodules, sedimentary rocks, and ores) are presented, which are in agreement with previously published data considering analytical uncertainties. Mantle-derived standard rock samples that are the source of iron for surficial, (bio)geochemical cycling yield a mean δ56Fe of 0.041 ± 0.11‰ ( n = 8; 2 SD) with reference to IRMM-14. Hydrothermal and metamorphic calcium carbonate rocks with a relatively low iron content (100-4000 ppm) have δ56Fe = -1.25 to -0.07‰. Structural Fe(II) in hydrothermal calcites has δ56Fe = -1.25 to -0.27‰. The light iron in this range of

  9. Approach for rapid extraction and speciation of mercury using a microtip ultrasonic probe followed by LC-ICP-MS.

    PubMed

    López, Isabel; Cuello, Susana; Cámara, Carmen; Madrid, Yolanda

    2010-07-15

    A fast method for mercury extraction from biological samples based on the use of HCl leaching plus different enzymatic hydrolysis (with and without mercury complexing agents), and the use of focussed ultrasounds (2-mm microtip) is here proposed. Total mercury content in several biological samples was determined by FI-ICP-MS using a carrier solution consisting of 0.1% (v/v) HCl, 0.1% (v/v) 2-mercaptoethanol, to avoid memory effect, and 0.15% (w/v) KCl. For mercury speciation a RP18 chromatographic column coupled to ICP-MS was used. A mobile phase consisting of 0.1% (v/v) formic acid, 0.1% (v/v) HFBA, 2% (v/v) methanol, and 0.02% (w/v) mM L-cysteine at pH 2.1 was used for chromatographic separation of the mercury species in the sample extracts. Extraction procedures were validated by using 50 mg of tuna fish tissue CRM-463 (2.85+/-0.16 mg kg(-1) for methylmercury). The recoveries obtained were 99+/-3% and 93+/-1% after acid leaching (HCl 7 M) and enzymatic extraction (15 mg protease type XIV in 2.5% (v/v) 2-mercaptoethanol), respectively. The optimal sonication conditions (5 min of exposure time and 40% of ultrasound amplitude) were applied to 5 mg of CRM-463 (88+/-5%), 5 mg of mussel tissue (81+/-11%) and to 2 mg of zebra fish embryos (90+/-10%) obtaining good recoveries in all cases. Methylmecury was found to be the most abundant Hg specie in all samples. The developed method is simple and rapid (5 min sample treatment); it is suitable for very small samples and does not alter the original form of the mercury species. Thus, it is of special interest in those cases in which validation of the results may often be hampered by lack of sample availability. PMID:20602941

  10. Ribonucleoside labeling with Os(VI): a methodological approach to evaluation of RNA methylation by HPLC-ICP-MS.

    PubMed

    Wrobel, Katarzyna; Rodríguez Flores, Crescencio; Chan, Qilin; Wrobel, Kazimierz

    2010-02-01

    Covalent modifications of nucleobases are thought to play an important role in regulating the functions of DNA and various cellular RNA types. Perhaps the best characterized is DNA methylation on cytosine (methyl tag attached to carbon 5 position) and such modification has also been detected in stable and long-lived RNA molecules. In this work, we propose a novel procedure enabling very sensitive quantification of methylcytidine and other ribonucleosides, based on reversed phase liquid chromatography with inductively coupled plasma mass spectrometry (ICP-MS) detection. The procedure relies on labeling ribose residues with osmium, by formation of a ternary complex between cis-diol ribose groups, hexavalent osmium (K(2)OsO(2)(OH)(4)) and tetramethylethylenediamine (TEMED). The derivatization reaction was carried out with 50 : 1 molar excess of Os to ribonucleoside, pH 4, for 2 h at room temperature. The structures of Os-labeled cytidine and methylcytidine were confirmed by electrospray ionization mass spectrometry. The separation of Os-labeled cytidine (C), uridine (U), 5-methylcytidine (5mC) and guanosine (G) was achieved on C18 column (Gemini, 150 × 3 mm, 5 μm) with isocratic elution (0.05% triethylamine + 6 mmol L(-1) ammonium acetate, pH 4.4: methanol (85 : 15)) and a total flow rate 0.6 mL min(-1). The column effluent was on-line introduced to ICP-MS (a model 7500 ce, Agilent Technologies) for specific detection at (189)Os. Calibration was performed within the concentration range 0-200 nmol L(-1) of each ribonucleoside and the analytical figures of merit were evaluated. For 100 μL injection, the detection limits for C, U, 5mC, G were 24, 38, 21 and 28 pmol L(-1), respectively. While introducing Os(vi)-TEMED to the column, it eluted in the dead volume and the detection limit for osmium was 20 pmol L(-1). The results obtained in this work might be helpful in the analysis of RNA digests, providing quantitative data on the ribonucleoside composition and

  11. Cross calibration between XRF and ICP-MS for high spatial resolution analysis of ombrotrophic peat cores for palaeoclimatic studies.

    PubMed

    Poto, Luisa; Gabrieli, Jacopo; Crowhurst, Simon; Agostinelli, Claudio; Spolaor, Andrea; Cairns, Warren R L; Cozzi, Giulio; Barbante, Carlo

    2015-01-01

    Ombrotrophic peatlands are remarkable repositories of high-quality climatic signals because their only source of nutrients is precipitation. Although several analytical techniques are available for analysing inorganic components in peat samples, they generally provide only low-resolution data sets. Here we present a new analytical approach for producing high-resolution data on main and trace elements from ombrotrophic peat cores. Analyses were carried out on a 7-m-long peat core collected from Danta di Cadore, North-Eastern Italy (46° 34' 16″ N, 12° 29' 58″ E). Ca, Ti, Cr, Fe, Cu, Zn, Ga, Sr, Y, Cd, Ba and Pb were detected at a resolution of 2.5 mm with a non-destructive X-ray fluorescence core scanner (XRF-CS). Calibration and quantification of the XRF-CS intensities was obtained using collision reaction cell inductively coupled plasma quadruple mass spectrometry (CRC-ICP-QMS). CRC-ICP-QMS measurements were carried out on discrete samples at a resolution of 1 cm, after dissolution of 150-mg aliquots with 9 ml HNO3 and 1 ml HF at 220 °C in a microwave system. We compare qualitative XRF-CS and quantitative CRC-ICP-MS data and, however the several sources of variability of the data, develop a robust statistical approach to determine the R (2) and the coefficient of a simple regression model together with confidence intervals. Perfect positive correlations were estimated for Cd, Cr, Pb, Sr, Ti and Zn; high positive correlations for Ba (0.8954), Y (0.7378), Fe (0.7349) and Cu (0.7028); while moderate positive correlations for Ga (0.5951) and Ca (0.5435). With our results, we demonstrate that XRF scanning techniques can be used, together with other well-established geochemical techniques (such as ICP-MS), to produce high-resolution (up to 2.5 mm) quantitative data from ombrotrophic peat bog cores.

  12. LA-ICP-MS analysis of isolated phosphatic grains indicates selective rare earth element enrichment during reworking and transport processes

    NASA Astrophysics Data System (ADS)

    Auer, Gerald; Reuter, Markus; Hauzenberger, Christoph A.; Piller, Werner E.

    2016-04-01

    Rare earth elements (REE) are a commonly used proxy to reconstruct water chemistry and oxygen saturation during the formation history of authigenic and biogenic phosphates in marine environments. In the modern ocean REE exhibit a distinct pattern with enrichment of heavy REE and strong depletion in Cerium. Studies of ancient phosphates and carbonates, however, showed that this 'modern' pattern is only rarely present in the geological past. Consequently, the wide range of REE enrichment patterns found in ancient marine phosphates lead to the proposition that water chemistry had to have been radically different in the earth's past. A wealth of studies has already shown that both early and late diagenesis can strongly affect REE signatures in phosphates and severely alter primary marine signals. However, no previous research was conducted on how alteration processes occurring prior to final deposition affect marine phosphates. Herein we present a dataset of multiple LA-ICP-MS measurements of REE signatures in isolated phosphate and carbonate grains deposited in a carbonate ramp setting in the central Mediterranean Sea during the middle Miocene "Monterey event". The phosphates are represented by authigenic, biogenic and detrital grains emplaced in bioclastic grain- to packstones dominated by bryozoan and echinoderm fragments, as well as abundant benthic and planktic foraminifers. The results of 39 grain specific LA-ICP-MS measurements in three discrete rock samples reveals four markedly different REE patterns (normalized to the Post Archean Australian Shale standard) in terms of total enrichment and pattern shape. Analyses of REE diagenesis proxies show that diagenetic alteration affected the samples only to a minor degree. Considering grain shape and REE patterns together indicate that authigenic, detrital and biogenic phosphates have distinct REE patterns irrespective of the sample. Our results show that the observed REE patterns in phosphates only broadly reflect

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

    PubMed

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

    2015-09-01

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

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

    PubMed

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

    2015-09-01

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

  15. LA-ICP-MS mapping of olivine from the Brahin and Brenham meteorites: Complex elemental distributions in the pallasite olivine precursor

    NASA Astrophysics Data System (ADS)

    McKibbin, Seann J.; O'Neill, Hugh St. C.; Mallmann, Guilherme; Halfpenny, Angela

    2013-10-01

    To investigate the early history of olivine from the Main-Group pallasites Brahin and Brenham, we have spatially mapped their trace-element distributions using laser-ablation inductively-coupled-plasma mass spectrometry (LA-ICP-MS). Brahin olivine interiors contain ∼100-200 μm patches enriched in Cr, Al, Ti, V, Sc and Ga, separated by linear enrichments of P; these structures bear no relation to current crystal morphologies. Rather, cross-cutting relationships suggest they predate olivine-metal mixing. Brenham olivine also has internal variations for these elements. By contrast, Ni and Co concentrations in olivine from both meteorites decrease near crystal margins, as expected for freezing-in of profiles formed during diffusive re-equilibration with metal during cooling. Brenham olivine also has decreasing Al, Cr and Ti near the margin. Correlations between concentrations of Cr and Al exist for individual Brahin olivine grains, but do not hold over multiple grains, indicating a heterogeneous precursor. Al and Ti are correlated over multiple grains in Brahin, interpreted as Ti cations decorating pre-existing Al-defects. In Brenham olivine, similar geochemical trends exist, but the Cr-Al relationship probably represents both grain margin effects and pre-existing internal heterogeneity. The preservation of structure for elements which are normally fast diffusers in olivine hinges on coupled substitutions involving Al, which along with P diffuses much more slowly than most other elements under some conditions. Al concentrations in olivine are low and variable (3-33 ppm) which is inconsistent with crystallisation from a normal silicate melt; Al-in-olivine thermometers indicate that pallasite olivine was formed in a low-temperature environment. Following its delivery to the magma ocean/core-mantle boundary, Al-P systematics were not substantially modified. Assuming diffusivities for Al and P that are similar to Si (since they reside in the same crystallographic site

  16. Did the massive magnetite "lava flows" of El Laco (Chile) form by magmatic or hydrothermal processes? New constraints from magnetite composition by LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Dare, Sarah A. S.; Barnes, Sarah-Jane; Beaudoin, Georges

    2015-06-01

    The El Laco magnetite deposits consist of more than 98 % magnetite but show field textures remarkably similar to mafic lava flows. Therefore, it has long been suggested that they represent a rare example of an effusive Fe oxide liquid. Field and petrographic evidence, however, suggest that the magnetite deposits represent replacement of andesite flows and that the textures are pseudomorphs. We determined the trace element content of magnetite by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) from various settings at El Laco and compared them with magnetite from both igneous and hydrothermal environments. This new technique allows us to place constraints on the conditions under which magnetite in these supposed magnetite "lava flows" formed. The trace element content of magnetite from the massive magnetite samples is different to any known magmatic magnetite, including primary magnetite phenocrysts from the unaltered andesite host rocks at El Laco. Instead, the El Laco magnetite is most similar in composition to hydrothermal magnetite from high-temperature environments (>500 °C), such as iron oxide-copper-gold (IOCG) and porphyry-Cu deposits. The magnetite trace elements from massive magnetite are characterised by (1) depletion in elements considered relatively immobile in hydrothermal fluids (e.g. Ti, Al, Cr, Zr, Hf and Sc); (2) enrichment in elements that are highly incompatible with magmatic magnetite (rare earth elements (REE), Si, Ca, Na and P) and normally present in very low abundance in magmatic magnetite; (3) high Ni/Cr ratios which are typical of magnetite from hydrothermal environments; and (4) oscillatory zoning of Si, Ca, Mg, REE and most high field strength elements, and zoning truncations indicating dissolution, similar to that formed in hydrothermal Fe skarn deposits. In addition, secondary magnetite in altered, brecciated host rock, forming disseminations and veins, has the same composition as magnetite from the massive

  17. Perspectives and perils of using U-Pb zircon geochronology to constrain stratigraphic age: lessons from the Permian-Triassic Karoo basin, South Africa

    NASA Astrophysics Data System (ADS)

    Weislogel, A. L.; Mckay, M. P.; Dean, J.; Fildani, A.

    2013-12-01

    The Karoo basin contains an important Carboniferous-Jurassic sedimentary record that chronicles the amalgamation of Pangea, subduction along the southern Panthallasan margin and later opening of the South Atlantic, Southern, and Indian oceans. It also preserves a robust record of the end-Permian extinction, Earth's largest paleobiologic crisis. Fortuitously, this stratigraphic record is interleaved with numerous air-fall volcanic ashes likely derived from a continental magmatic system, part of which is currently exposed in the Choiyoi igneous province of South America. Our U-Pb geochronology of air-fall ash zircon from the Ecca and Beaufort Groups via SHRIMP analysis, along with LA-ICP-MS U-Pb analysis of detrital zircon from interbedded sandstones indicate that magmatic activity of this system likely persisted for at least 50 Ma. Particularly noteworthy is that uppermost Ecca Group detrital zircon signature exhibits few Precambrian ages and abundant Permian-Triassic ages; thus, by the start of marginal marine deposition, Karoo basin clastic influx was primarily sourced by some part of the Permian-Triassic Panthallassic magmatic system (i.e., the Choiyoi igneous province or its southern equivalent). Detrital zircon U-Pb ages suggest initial zircon formed within this magmatic system by ~300 Ma and that the apex of zircon crystallization occurred at ~265-275 Ma, after which, zircon crystallization decreased through time. We hypothesize that over the long duration of magmatic evolution, the melt began to become depleted with respect to zircon, such that by ~260 Ma, the melt became primarily undersaturated with respect to zircon. As a result, zircon was no longer a major accessory phase and ultimately after ~250 Ma was extruded only in scant trace amounts. This interpretation is also supported by U-Pb zircon geochronology on a few dozen Ecca and Beaufort Group ashes from across the Karoo basin. Individual ash ages were determined from statistically-robust, coherent

  18. Online monitoring of nanoparticles formed during nanosecond laser ablation

    NASA Astrophysics Data System (ADS)

    Nováková, Hana; Holá, Markéta; Vojtíšek-Lom, Michal; Ondráček, Jakub; Kanický, Viktor

    2016-11-01

    The particle size distribution of dry aerosol originating from laser ablation of glass material was monitored simultaneously with Laser Ablation - Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) analysis and two aerosol spectrometers - Fast Mobility Particle Sizer (FMPS) and Aerodynamic Particle Sizer (APS). The unique combination of LA-ICP-MS and FMPS offers the possibility of measuring the particle size distribution every 1 s of the ablation process in the size range of 5.6-560 nm. APS extends the information about particle concentration in the size range 0.54-17 μm. Online monitoring of the dry aerosol was performed for two ablation modes (spot and line with a duration of 80 s) with a 193 nm excimer laser system, using the glass reference material NIST 610 as a sample. Different sizes of laser spot for spot ablation and different scan speeds for line ablation were tested. It was found that the FMPS device is capable of detecting changes in particle size distribution at the first pulses of spot laser ablation and is suitable for laser ablation control simultaneously with LA-ICP-MS analysis. The studied parameters of laser ablation have an influence on the resulting particle size distribution. The line mode of laser ablation produces larger particles during the whole ablation process, while spot ablation produces larger particles only at the beginning, during the ablation of the intact layer of the ablated material. Moreover, spot ablation produces more primary nano-particles (in ultrafine mode size range < 100 nm) than line ablation. This effect is most probably caused by a reduced amount of large particles released from the spot ablation crater. The larger particles scavenge the ultrafine particles during the line ablation mode.

  19. The absence of lithium isotope fractionation during basalt differentiation: New measurements by multicollector sector ICP-MS

    USGS Publications Warehouse

    Tomascak, P.B.; Tera, F.; Helz, R.T.; Walker, R.J.

    1999-01-01

    We report measurements of the isotopic composition of lithium in basalts using a multicollector magnetic sector plasma-source mass spectrometer (MC-ICP-MS). This is the first application of this analytical technique to Li isotope determination. External precision of multiple replicate and duplicate measurements for a variety of sample types averages ??1.1??? (2?? population). The method allows for the rapid (???8 min/sample) analysis of small samples (???40 ng Li) relative to commonly used thermal ionization methods. The technique has been applied to a suite of samples from Kilauea Iki lava lake, Hawaii. The samples range from olivine-rich cumulitic lava to SiO2 - and K2O-enriched differentiated liquids, and have ??7Li (per mil deviation of sample 7Li/6Li relative to the L-SVEC standard) of +3.0 to +4.8. The data indicate a lack of per mil-level Li isotope fractionation as a result of crystal-liquid fractionation at temperatures greater than 1050??C. This conclusion has been tacitly assumed but never demonstrated, and is important to the interpretation of Li isotope results from such geochemically complex environments as island arcs. Copyright ?? 1999 Elsevier Science Ltd.

  20. Hair Mercury Levels Detection in Fishermen from Sicily (Italy) by ICP-MS Method after Microwave-Assisted Digestion

    PubMed Central

    Giangrosso, Giuseppe; Cammilleri, Gaetano; Macaluso, Andrea; Vella, Antonio; D'Orazio, Nicolantonio; Graci, Stefania; Lo Dico, Gianluigi Maria; Galvano, Fabio; Giangrosso, Margherita; Ferrantelli, Vincenzo

    2016-01-01

    A number of ninety-six hair samples from Sicilian fishermen were examined for total mercury detection by an Inductively Coupled Plasma Mass Spectrometry (ICP-MS) method. The mercury levels obtained were compared with mercury levels of 96 hair samples from a control group, in order to assess potential exposure to heavy metals of Sicilian fishermen due to fish consumption and closeness to industrial activities. Furthermore, the mercury levels obtained from hair samples were sorted by sampling area in order to verify the possible risks linked to the different locations. The overall mean concentration in the hair of the population of fishermen was 6.45 ± 7.03 μg g−1, with a highest value in a fisherman of Sciacca (16.48 μg g−1). Hair mercury concentration in fishermen group was significantly higher than in control group (p < 0.01). There was no significant difference in hair total mercury concentrations between sampling areas (p > 0.05). The results of this study indicate a greater risk of exposure to mercury in Sicilian fishermen, in comparison to the control population, due to the high consumption of fish and the close relationship with sources of exposure (ports, dumps, etc.). PMID:27127456

  1. 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.

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

    PubMed Central

    Lin, Yunfeng

    2015-01-01

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

  3. Automated sample preparation for radiogenic and non-traditional metal isotope analysis by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Field, M. P.; Romaniello, S. J.; Gordon, G. W.; Anbar, A. D.

    2012-12-01

    High throughput analysis is becoming increasingly important for many applications of radiogenic and non-traditional metal isotopes. While MC-ICP-MS instruments offer the potential for very high sample throughout, the requirement for labor-intensive sample preparation and purification procedures remains a substantial bottleneck. Current purification protocols require manually feeding gravity-driven separation columns, a process that is both costly and time consuming. This bottleneck is eliminated with the prepFAST-MC™, an automated, low-pressure ion exchange chromatography system that can process from 1 to 60 samples in unattended operation. The syringe-driven system allows sample loading, multiple acid washes, column conditioning and elution cycles necessary to isolate elements of interest and automatically collect up to 3 discrete eluent fractions at user-defined intervals (time, volume and flow rate). Newly developed protocols for automated purification of uranium illustrates high throughput (>30 per run), multiple samples processed per column (>30), complete (>99%) matrix removal, high recovery (> 98%, n=25), and excellent precision (2 sigma =0.03 permil, n=10). The prepFAST-MC™ maximizes sample throughput and minimizes costs associated with personnel and consumables providing an opportunity to greatly expand research horizons in fields where large isotopic data sets are required, including archeology, geochemistry, and climate/environmental science

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

    PubMed

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

    2007-06-01

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

  5. Characterization of saline groundwater at Horonobe, Hokkaido, Japan by SEC-UV-ICP-MS: speciation of uranium and iodine.

    PubMed

    Kozai, Naofumi; Ohnuki, Toshihiko; Iwatsuki, Teruki

    2013-03-15

    The saline groundwater collected at a depth of about 500 m in Horonobe, Japan, where an underground research laboratory (URL) has been built, is rich in saline (Na 4900 ppm, Cl 7600 ppm), iodine (42 ppm), and methane gas. We analyzed the colloids and ions of this groundwater mainly by employing a size exclusion chromatography (SEC) coupled on-line to ultraviolet-visible (UV-Vis) detection and inductively coupled plasma mass spectrometry (ICP-MS) technique and focused on the speciation of uranium and iodine, both of which are of particular importance for radioactive waste disposal. For this purpose, the groundwater sample was introduced to SEC columns after being passed through a 0.45 μm filter but without further pretreatment, such as isolation of colloids. The chromatographic profiles obtained with two different SEC columns were compared. This study revealed that uranium present in the groundwater at several tens of ppt was associated with low molecular weight silica species with neutral charge. The silica species were virtually free of metal elements such as Na, K, Mg, Ca, and Al. This study also found that almost all of the iodine in the groundwater was iodide (I(-)). The groundwater contained an unidentified organic colloid that was not a carrier for the radioactive waste-relevant elements Se, Sr, I, Cs, Th, and U.

  6. The production of ultra-high purity single isotopes or tailored isotope mixtures by ICP-MS

    SciTech Connect

    Liezers, Martin; Farmer, Orville T.; Dion, Michael P.; Thomas, Linda MP; Eiden, Gregory C.

    2015-01-01

    We report the development and testing of a simple collector arrangement for a commercial quadrupole ICP-MS that for the first time has been used to produce small quantities of highly enriched (>99.99%) single isotopes, with deposition rates >10 ng/hour. The collector assembly replaces the standard instrument detector allowing for implantation with simultaneous monitoring of the incident ion current. Even under zero bias implant conditions, low energy (<10 eV), ion collection efficiency was observed to be very high ~99%. 151Eu ion currents of 0.1-0.5 nA were collected on a simple, planar foil without resorting to any type of cup configuration. Recovery of the enriched isotope from such foils is much simpler than from a more complex cup configuration. High rejection of adjacent mass isotopes was demonstrated by selectively implanting 167Er without any discernible co-implantation of 166Er and 168Er. The important analytical possibilities of the new approach to isotope ratio measurement, tracer purification and radiation measurements are discussed.

  7. Speciation analysis of antimony in extracts of size-classified volcanic ash by HPLC-ICP-MS.

    PubMed

    Miravet, R; López-Sánchez, J F; Rubio, R; Smichowski, P; Polla, G

    2007-03-01

    Although there is concern about the presence of toxic elements and their species in environmental matrices, for example water, sediment, and soil, speciation analysis of volcanic ash has received little attention. Antimony, in particular, an emerging element of environmental concern, has been less studied than other potentially toxic trace elements. In this context, a study was undertaken to assess the presence of inorganic Sb species in ash emitted from the Copahue volcano (Argentina). Antimony species were extracted from size-classified volcanic ash (<36 microm, 35-45 microm, 45-150 microm, and 150-300 microm) by use of 1 mol L(-1) citrate buffer at pH 5. Antimony(III) and (V) in the extracts were separated and quantified by high-performance liquid chromatography combined on-line with inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Antimony species concentrations (microg g(-1)) in the four fractions varied from 0.14 to 0.67 for Sb(III) and from 0.02 to 0.03 for Sb(V). The results reveal, for the first time, the occurrence of both inorganic Sb species in the extractable portion of volcanic ash. Sb(III) was always the predominant species.

  8. Arsenic, Antimony, Chromium, and Thallium Speciation in Water and Sediment Samples with the LC-ICP-MS Technique

    PubMed Central

    Jabłońska-Czapla, Magdalena

    2015-01-01

    Chemical speciation is a very important subject in the environmental protection, toxicology, and chemical analytics due to the fact that toxicity, availability, and reactivity of trace elements depend on the chemical forms in which these elements occur. Research on low analyte levels, particularly in complex matrix samples, requires more and more advanced and sophisticated analytical methods and techniques. The latest trends in this field concern the so-called hyphenated techniques. Arsenic, antimony, chromium, and (underestimated) thallium attract the closest attention of toxicologists and analysts. The properties of those elements depend on the oxidation state in which they occur. The aim of the following paper is to answer the question why the speciation analytics is so important. The paper also provides numerous examples of the hyphenated technique usage (e.g., the LC-ICP-MS application in the speciation analysis of chromium, antimony, arsenic, or thallium in water and bottom sediment samples). An important issue addressed is the preparation of environmental samples for speciation analysis. PMID:25873962

  9. Evaluation strategies and uncertainty calculation of isotope amount ratios measured by MC ICP-MS on the example of Sr.

    PubMed

    Horsky, Monika; Irrgeher, Johanna; Prohaska, Thomas

    2016-01-01

    This paper critically reviews the state-of-the-art of isotope amount ratio measurements by solution-based multi-collector inductively coupled plasma mass spectrometry (MC ICP-MS) and presents guidelines for corresponding data reduction strategies and uncertainty assessments based on the example of n((87)Sr)/n((86)Sr) isotope ratios. This ratio shows variation attributable to natural radiogenic processes and mass-dependent fractionation. The applied calibration strategies can display these differences. In addition, a proper statement of uncertainty of measurement, including all relevant influence quantities, is a metrological prerequisite. A detailed instructive procedure for the calculation of combined uncertainties is presented for Sr isotope amount ratios using three different strategies of correction for instrumental isotopic fractionation (IIF): traditional internal correction, standard-sample bracketing, and a combination of both, using Zr as internal standard. Uncertainties are quantified by means of a Kragten spreadsheet approach, including the consideration of correlations between individual input parameters to the model equation. The resulting uncertainties are compared with uncertainties obtained from the partial derivatives approach and Monte Carlo propagation of distributions. We obtain relative expanded uncertainties (U rel; k = 2) of n((87)Sr)/n((86)Sr) of < 0.03 %, when normalization values are not propagated. A comprehensive propagation, including certified values and the internal normalization ratio in nature, increases relative expanded uncertainties by about factor two and the correction for IIF becomes the major contributor.

  10. Hair Mercury Levels Detection in Fishermen from Sicily (Italy) by ICP-MS Method after Microwave-Assisted Digestion.

    PubMed

    Giangrosso, Giuseppe; Cammilleri, Gaetano; Macaluso, Andrea; Vella, Antonio; D'Orazio, Nicolantonio; Graci, Stefania; Lo Dico, Gianluigi Maria; Galvano, Fabio; Giangrosso, Margherita; Ferrantelli, Vincenzo

    2016-01-01

    A number of ninety-six hair samples from Sicilian fishermen were examined for total mercury detection by an Inductively Coupled Plasma Mass Spectrometry (ICP-MS) method. The mercury levels obtained were compared with mercury levels of 96 hair samples from a control group, in order to assess potential exposure to heavy metals of Sicilian fishermen due to fish consumption and closeness to industrial activities. Furthermore, the mercury levels obtained from hair samples were sorted by sampling area in order to verify the possible risks linked to the different locations. The overall mean concentration in the hair of the population of fishermen was 6.45 ± 7.03 μg g(-1), with a highest value in a fisherman of Sciacca (16.48 μg g(-1)). Hair mercury concentration in fishermen group was significantly higher than in control group (p < 0.01). There was no significant difference in hair total mercury concentrations between sampling areas (p > 0.05). The results of this study indicate a greater risk of exposure to mercury in Sicilian fishermen, in comparison to the control population, due to the high consumption of fish and the close relationship with sources of exposure (ports, dumps, etc.). PMID:27127456

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

    NASA Astrophysics Data System (ADS)

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

    2006-03-01

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

  12. Thallium (III) determination in the Baltic seawater samples by ICP MS after preconcentration on SGX C18 modified with DDTC.

    PubMed

    Krasnodębska-Ostręga, Beata; Sadowska, Monika; Piotrowska, Katarzyna; Wojda, Marta

    2013-08-15

    The main difficulty of speciation analysis of thallium lies in extremely low concentrations of Tl(III) in comparison to Tl(I), which is the dominating form of thallium in environmental samples. In this study, a sensitive method is presented for separation of trace amounts of Tl(III) from Tl(I) and preconcentration of Tl(III) using octadecyl silica gel modified with diethyldithiocarbamate (DDTC). Under optimal conditions, only Tl(III) is retained on the sorbent, and then eluted with 96% ethanol. After chemical decomposition of Tl(III)-DDTC complex, thallium is determined by inductively coupled plasma mass spectrometry. High performance liquid chromatography with ICP MS detection was used to control the correctness of the obtained results. Parameters affecting solid phase extraction (SPE) such as pH, type, concentration and volume of eluent, breakthrough volume, and the impact of sample salinity (chlorides) and other interfering ions (Cd(II), Zn(II), Pb(II), Cu(II), Sn(II)) were investigated. The limit of detection (LOD), evaluated for 2 mL of sample solution, was 0.10 ng for Tl(I) and 0.43 ng for Tl(III). The method was applied to the determination of Tl(I) and Tl(III) in the Baltic seawater samples enriched in both thallium species.

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

    PubMed

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

    2007-06-01

    An inductively coupled plasma mass spectrometry (ICP-MS) for determination of the contents of 8 trace heavy metal elements in cortex Phellodendron chinense after microwave-assisted digestion of the sample has been developed. The accuracy of the method was evaluated by the analysis of corresponding trace heavy metal elements in standard reference materials (GBW 07604 and GBW 07605). By applying the proposed method, the contents of 8 trace heavy metal elements in cortex Phellodendron chinense cultivated in different areas (in Bazhong, Yibin and Yingjing, respectively) of Sichuan and different growth period (6, 8 and 10 years of samples from Yingjing) were determined. The relative standard deviation (RSD) is in the range of 3.2%-17.8% and the recoveries of standard addition are in the range of 70%-120%. The results of the study indicate that the proposed method has the advantages of simplicity, speediness and sensitivity. It is suitable for the determination of the contents of 8 trace heavy metal elements in cortex Phellodendron chinense. The results also show that the concentrations of 4 harmful trace heavy metal elements As, Cd, Hg and Pb in cortex Phellodendron chinense are all lower than the limits of Chinese Pharmacopoeia and Green Trade Standard for Importing and Exporting Medicinal Plant and Preparation. Therefore, the cortex Phellodendron chinense is fit for use as medicine and export. PMID:17763791

  14. Use of ICP/MS with ultrasonic nebulizer for routine determination of uranium activity ratios in natural water

    USGS Publications Warehouse

    Kraemer, T.F.; Doughten, M.W.; Bullen, T.D.

    2002-01-01

    A method is described that allows precise determination of 234U/238U activity ratios (UAR) in most natural waters using commonly available inductively coupled plasma/mass spectrometry (ICP/MS) instrumentation and accessories. The precision achieved by this technique (??0.5% RSD, 1 sigma) is intermediate between thermal ionization mass spectrometry (??0.25% RSID, 1 sigma) and alpha particle spectrometry (??5% RSD, 1 sigma). It is precise and rapid enough to allow analysis of a large number of samples in a short period of time at low cost using standard, commercially available quadrupole instrumentation with ultrasonic nebulizer and desolvator accessories. UARs have been analyzed successfully in fresh to moderately saline waters with U concentrations of from less than 1 ??g/L to nearly 100 ??g/L. An example of the uses of these data is shown for a study of surface-water mixing in the North Platte River in western Nebraska. This rapid and easy technique should encourage the wider use of uranium isotopes in surface-water and groundwater investigations, both for qualitative (e.g. identifying sources of water) and quantitative (e.g. determining end-member mixing ratios purposes.

  15. Determination of water-soluble and insoluble elements in PM2.5 by ICP-MS.

    PubMed

    Manousakas, M; Papaefthymiou, H; Eleftheriadis, K; Katsanou, K

    2014-09-15

    The elemental composition of water-soluble and acid-soluble fractions of PM2.5 samples from two different Greek cities (Patras and Megalopolis) was investigated. Patras and Megalopolis represent different environments. Specifically, Patras is an urban environment with proximity to a large port, while Megalopolis is a small city located close to lignite power plants. Both cities can serve as a representative example of European cities with similar characteristics. The concentration of 14 elements (As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Fe, Sr, Ti, V and Zn) was determined in each fraction by ICP-MS. Microwave assisted digestion was used to digest the samples using a mixture of HNO3 and HF. For the determination of the water soluble fraction, water was chosen as the simplest and most universal extraction solvent. For the validation of the extraction procedure, the recoveries were tested on two certified reference materials (NIST SRM 1648 Urban Particulate Matter and NIST 1649a Urban Dust). Results showed that Zn has the highest total concentration (273 and 186 ng/m(3)) and Co the lowest (0.48 and 0.23 ng/m(3)) for Patras and Megalopolis samples, respectively. Nickel with 65% for Patras and As with 49% for Megalopolis displayed the highest solubility, whereas Fe (10%) and Ti (2%) the lowest ones, respectively.

  16. [Determination of elements related to reducing blood sugar (ERBS) in tea and tea polysaccharide by ICP-MS].

    PubMed

    Xie, Ming-Yong; Nie, Shao-Ping; Fu, Bo-Qiang; Wang, Xiao-Ru

    2006-09-01

    Contents of elements related to reducing blood sugar (ERBS) in several kinds of green tea of Wuyuan county, their tea infusion extracted by warm water and boiling water and tea polysaccharide (TP) were determined by ICP-MS, after the samples were digested with acids by microwave method. The relation between the amount of ERBS and tea quality and the relation between the content of ERBS in TP and the total content in tea were discussed. The results showed that the amounts of ERBS in tea and TP are different in various samples. The amount of ERBS in TP extracted from coarse tea was higher than that from fresh tea. The percentage of certain ERBS in TP accounting for the ERBS in tea ranged from 0.03% to 9.57%. As to the total ERBS in TP extracted from Mt. Zhang super grade tea and grade 5 tea, the percentages were 1.11% and 2.10% respectively. As to Mt. Gu old tea, it was 0.85%. The results could provide data for selecting tea material used to extracting tea polysaccharide and for studying the mechanism of reducing blood sugar. PMID:17112052

  17. Tracing source terranes using U-Pb-Hf isotopic analysis of detrital zircons: provenance of the Orhanlar Unit of the Palaeotethyan Karakaya subduction-accretion complex, NW Turkey

    NASA Astrophysics Data System (ADS)

    Ustaömer, Timur; Ayda Ustaömer, Petek; Robertson, Alastair; Gerdes, Axel

    2016-04-01

    -inductively coupled plasma-mass spectrometer (LA-MC-ICP-MS) at Goethe University, Frankfurt. A total of 399 U-Pb spot analyses were carried out on zircons from the sandstones of the Orhanlar Unit. 84% of the data yielded Precambrian ages, which is in marked contrast with the typical arkosic sandstones of the Karakaya Complex in which Precambrian zircons form only 10% of the population. Three zircon grains of Ladinian age suggest a maximum depositional age for the Orhanlar Unit. The most prominent zircon population is of Ediacaran-Cryogenian age (31%). The second largest population is Tonian-Stenian (22%), the third largest Cryogenian-Tonian (9%) and the fourth Devonian-Carboniferous (7%). There are also minor zircon populations of Palaeoproterozoic and Neo-Archean ages. The Precambrian zircon populations in the Orhanlar Unit sandstones are identical to those in the schists of the Sakarya continental crust (P.A. Ustaömer et al. 2012; this study). Their Hf isotope compositions also overlap, suggesting that the Sakarya continental crust could be a source for the sandstones of the Orhanlar Unit. On the other hand, the Hf(t) values of most of the Devonian and Carboniferous detrital zircons differ from those of the Devonian and Carboniferous granites that intrude the Sakarya continental crust. The Karakaya Complex as a whole appears to have been derived from two different source terranes, of which the Orhanlar Unit sandstones represent a minor, but significant component. Possible explanations are that two different source terranes already existed in the same region but that these were not exposed to erosion at the same time or, if exposed simultaneously, experienced different depositional pathways (without mixing); alternatively, the Orhanar Unit represents part of a different tectono-stratigraphic terrane from the other Karakaya Complex units, with which it was tectonically amalgamated prior to Early Jurassic deposition of a common sedimentary cover. Ustaömer PA, Ustaömer T

  18. Tracing source terranes using U-Pb-Hf isotopic analysis of detrital zircons: provenance of the Orhanlar Unit of the Palaeotethyan Karakaya subduction-accretion complex, NW Turkey

    NASA Astrophysics Data System (ADS)

    Ustaömer, Timur; Ayda Ustaömer, Petek; Robertson, Alastair; Gerdes, Axel

    2016-04-01

    -inductively coupled plasma-mass spectrometer (LA-MC-ICP-MS) at Goethe University, Frankfurt. A total of 399 U-Pb spot analyses were carried out on zircons from the sandstones of the Orhanlar Unit. 84% of the data yielded Precambrian ages, which is in marked contrast with the typical arkosic sandstones of the Karakaya Complex in which Precambrian zircons form only 10% of the population. Three zircon grains of Ladinian age suggest a maximum depositional age for the Orhanlar Unit. The most prominent zircon population is of Ediacaran-Cryogenian age (31%). The second largest population is Tonian-Stenian (22%), the third largest Cryogenian-Tonian (9%) and the fourth Devonian-Carboniferous (7%). There are also minor zircon populations of Palaeoproterozoic and Neo-Archean ages. The Precambrian zircon populations in the Orhanlar Unit sandstones are identical to those in the schists of the Sakarya continental crust (P.A. Ustaömer et al. 2012; this study). Their Hf isotope compositions also overlap, suggesting that the Sakarya continental crust could be a source for the sandstones of the Orhanlar Unit. On the other hand, the Hf(t) values of most of the Devonian and Carboniferous detrital zircons differ from those of the Devonian and Carboniferous granites that intrude the Sakarya continental crust. The Karakaya Complex as a whole appears to have been derived from two different source terranes, of which the Orhanlar Unit sandstones represent a minor, but significant component. Possible explanations are that two different source terranes already existed in the same region but that these were not exposed to erosion at the same time or, if exposed simultaneously, experienced different depositional pathways (without mixing); alternatively, the Orhanar Unit represents part of a different tectono-stratigraphic terrane from the other Karakaya Complex units, with which it was tectonically amalgamated prior to Early Jurassic deposition of a common sedimentary cover. Ustaömer PA, Ustaömer T

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

    PubMed

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

    2015-01-01

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

  20. Provenance from zircon U-Pb age distributions in crustally contaminated granitoids

    NASA Astrophysics Data System (ADS)

    Bahlburg, Heinrich; Berndt, Jasper

    2016-05-01

    The basement of sedimentary basins is often entirely covered by a potentially multi-stage basin fill and therefore removed from direct observation and sampling. Melts intruding through the basin stratigraphy at a subsequent stage in the geological evolution of a region may assimilate significant volumes of country rocks. This component may be preserved in the intrusive body either as xenoliths or it may be reflected only by the age spectrum of incorporated zircons. Here we present the case of an Ordovician calc-alkaline intrusive belt in NW Argentina named the "Faja Eruptiva de la Puna Oriental" (Faja Eruptiva), which in the course of intrusion sampled the unexposed and unknown basement of the Ordovician basin in this region, and parts of the basin stratigraphy. We present new LA-ICP-MS U-Pb ages on zircons from 9 granodiorites and granites of the Faja Eruptiva. The main part of the Faja Eruptiva intruded c. 445 Ma in the Late Ordovician. The zircon ages obtained from the intrusive rocks have a large spread between 2683.5 ± 21.6 and 440.0 ± 4.9 Ma and reflect the underlying crust and may be interpreted in several ways. The inherited zircons may have been derived from the oldest known unit in the region, the thick siliciclastic turbidite successions of the upper Neoproterozoic-lower Cambrian Puncoviscana Formation, which is inferred to represent the basement of the NW Argentina. The basement to the Puncoviscana Formation is not known. Alternatively, the inherited zircons may reflect the geochronological structure of the entire unexposed Early Paleozoic crust underlying this region of which the Puncoviscana Formation was only one component. This crust likely contained rocks pertaining to and detritus derived from earlier orogenic cycles of the southwestern Amazonia craton, including sources of Early Meso- and Paleoproterozoic age. Detritus derived, in turn, from the Faja Eruptiva intrusive belt reflects the origin of the granitoids as well as the inherited

  1. U-Pb Detrital Zircon Geochronology and Implications: the Mesozoic southern Ordos Basin, North Central China

    NASA Astrophysics Data System (ADS)

    Xie, X.; Heller, P. L.; Chamberlain, K. R.

    2007-12-01

    Two deformation belts -- the Qinling orogenic belt (QOB) to the south and the Western Liupanshan thrust belt (WLTB) to the west, including the Qilian-Qaidam terrane (QQT) -- control the evolution of the southern Ordos Basin during early Mesozoic time. U-Pb detrital zircon geochronology is used to identify provenance, reconstruct paleogeography, and document the relative timing of basin margin deformation. Two correlated strata same age samples of the Middle to Late Triassic Yanchang Fm. were collected from the southern and southwestern basin margin respectively. In total 258 zircon grains were analyzed using LA-ICP-MS. Three major age populations -- 240-490 Ma, 1.8-2.0 Ga, and 2.2-2.8 Ga -- characterize the detrital zircon grains of the Yanchang Fm. Regional geochronology studies show that the two oldest age groups match ages of basement rocks found in the underlying North China block. The younger age group can be subdivided into three distinctive groups: 240-300 Ma, 300-400, and 400-490 Ma. The youngest age group matches ages exposed to the west in the QQT, whereas the other two match grains from southern QOB source. In all samples detrital zircon from the WLTB source area overwhelms the QOB source, regardless of its proximity to either basin margin. This result suggests that either the source rock with the youngest zircon grains (e.g. 240- 490 Ma) from the QOB to the south have been eroded away and no longer existed, or simply the QOB, even during deformation, was never the dominant source of detrital zircon to the southern Ordos Basin. Probably some drainage systems far from the west combine with some local tributary systems from the south control the sedimentation in the south Ordos Basin during the middle to Late Triassic time. This is surprising in that most studies suggest that the QOB was a longer lived and more dominant tectonic feature in this part of China during early Mesozoic time. Furthermore, it also indicates that: 1) deformation in the QOB and WLTB

  2. Ion Microprobe U-Pb Dating of Zagami Phosphates

    NASA Astrophysics Data System (ADS)

    Sano, Y.; Koike, M.; Takahata, N.; Terada, K.

    2016-08-01

    We report U-Pb dating of Zagami phosphates using SHRIMP and NanoSIMS. A least-squares fit gives 238U-206Pb isochron age of 363 ± 120 Ma and total Pb/U age of 300 ± 84 Ma, which are older than 180 ± 7 Ma of baddeleyite of Zagami in literature.

  3. Geochemistry: does U-Pb date Earth's core formation?

    PubMed

    Yin, Qing-zhu; Jacobsen, Stein B

    2006-11-01

    Constraining the timing of the formation of Earth's core, which defines the birth of our planet, is essential for understanding the early evolution of Earth-like planets. Wood and Halliday and Halliday discuss the apparent discrepancy between the U-Pb (60-80 Myr) and Hf-W clocks (30 Myr) in determining the timescale of Earth's accretion and core formation. We find that the information the authors present is at times contradictory (for example, compare Fig. 1 in ref. 1 with Fig. 1 in ref. 2) and confusing and could suggest that the U-Pb clock constrains core formation better than the Hf-W system. Here we point out the limitations of the U-Pb system and show that the U-Pb age cannot be used to argue for protracted accretion and/or core formation (>50 Myr) because this clock only records the processes that occurred during the last 1% of Earth's accretion and core formation in the Wood and Halliday mechanism.

  4. Paleocene and Early Eocene volcanic ash layers in the Schlieren Flysch, Switzerland: U-Pb dating and Hf-isotopes of zircons, pumice geochemistry and origin

    NASA Astrophysics Data System (ADS)

    Koch, Simone; Winkler, Wilfried; Von Quadt, Albrecht; Ulmer, Peter

    2015-11-01

    Thin mm to cm thick bentonite layers of Paleocene to Early Eocene age in the Tonsteinschichten of the Schlieren Flysch represent volcanic ash layers. Heavy mineral analysis of the layers indicates basic to acidic volcanic sources. U/Pb dating of single zircon crystals of a Paleocene layer (WW1948) by LA-ICP-MS points to an eruption at 59.87 ± 0.41 Ma, whereas ID-TIMS shows an eruption age of 60.96 ± 0.07 Ma. Taking into account the external precision of LA-ICP-MS analyses of 1-2% both ages are overlapping and indicate an apparent minimal durations of zircon crystallization of 350 ka. Hf-isotope analysis of the same zircon crystals reveals the hybrid character of the source magma. The geochemical composition of the pumice grains of all bentonite layers is strongly affected by alteration. Nevertheless, the original character of the volcanic source can be evaluated. The Paleocene ashes (Lower Tonsteinschichten, LT) show a more fractionated multi-element pattern than the ashes of Early Eocene (Upper Tonsteinschichten, UT). The LT ash series are of rhyodacite to dacite character whereas the UT ashes fall in the field of alkali basalts. Both ash series seem to originate from a within-plate volcanic setting according to their trace element concentrations. Geochemical and temporary counterparts can be found in ash layers from Anthering (Austria) and the Danish Basin. As proposed for those ashes, volcanism connected to the opening of the North Atlantic might be the source as well for the ashes in the Schlieren Flysch. By comparison of the composition of rocks from the British Paleogene Igneous Province BPIP and the Schlieren Flysch ashes many correlations can be drawn which supports the suggestion of a North Atlantic origin of the Alpine ashes.

  5. U-Pb SHRIMP dating of uraniferous opals

    USGS Publications Warehouse

    Nemchin, A.A.; Neymark, L.A.; Simons, S.L.

    2006-01-01

    U-Pb and U-series analyses of four U-rich opal samples using sensitive high-resolution ion microprobe (SHRIMP) demonstrate the potential of this technique for the dating of opals with ages ranging from several tens of thousand years to millions of years. The major advantages of the technique, compared to the conventional thermal ionisation mass spectrometry (TIMS), are the high spatial resolution (???20 ??m), the ability to analyse in situ all isotopes required to determine both U-Pb and U-series ages, and a relatively short analysis time which allows obtaining a growth rate of opal as a result of a single SHRIMP session. There are two major limitations to this method, determined by both current level of development of ion probes and understanding of ion sputtering processes. First, sufficient secondary ion beam intensities can only be obtained for opal samples with U concentrations in excess of ???20 ??g/g. However, this restriction still permits dating of a large variety of opals. Second, U-Pb ratios in all analyses drifted with time and were only weakly correlated with changes in other ratios (such as U/UO). This drift, which is difficult to correct for, remains the main factor currently limiting the precision and accuracy of the U-Pb SHRIMP opal ages. Nevertheless, an assumption of similar behaviour of standard and unknown opals under similar analytical conditions allowed successful determination of ages with precisions of ???10% for the samples investigated in this study. SHRIMP-based U-series and U-Pb ages are consistent with TIMS dating results of the same materials and known geological timeframes. ?? 2005 Elsevier B.V. All rights reserved.

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

    PubMed

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

    2015-01-01

    A single-laboratory validation (SLV) is presented for the simultaneous determination of 10 ultratrace elements (UTEs) including aluminum (Al), arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), mercury (Hg), molybdenum (Mo), lead (Pb), selenium (Se), and tin (Sn) in infant formulas, adult nutritionals, and milk based products by inductively coupled plasma (ICP)/MS after acidic pressure digestion. This robust and routine multielemental method is based on several official methods with modifications of sample preparation using either microwave digestion or high pressure ashing and of analytical conditions using ICP/MS with collision cell technology. This SLV fulfills AOAC method performance criteria in terms of linearity, specificity, sensitivity, precision, and accuracy and fully answers most international regulation limits for trace contaminants and/or recommended nutrient levels established for 10 UTEs in targeted matrixes. PMID:26268978

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

    PubMed

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

    2015-01-01

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

  8. Determination of trace elements in rape honey and its corresponding rape flower and stem by ICP-MS.

    PubMed

    Chen, Hui; Wang, Zhi-Bin; Chang, Qiao-Ying; Wang, Wei; Fan, Chun-Lin; Pang, Guo-Fang

    2014-02-01

    The determination of 10 trace elements including Na, Mg, P, K, Ca, Mn, Zn, Rb, Sr and Ba, in rape honey and its corresponding rape flower and stem gathered from nine sampling sites was carried out by inductively coupled plasma mass spectrometry (ICP-MS). The contents of K, P, Ca, Mg and Na were obviously higher than Zn, Rb, Mn, Sr and Ba in rape honey, rape flower and rape stem. For the first five elements, K had the highest content, followed by P, Ca, Mg and Na. However, the order of content for latter five elements was not the same in different matrixes. The contents of K, P and Ca were all higher than 1 000 mg x kg(-1) in rape flower and rape stem, while the contents of P, Ca, Mn, Zn and Rb in rape flower were slightly higher than in rape stem. It can be concluded that rape flower showed slightly higher concentrating ability for trace elements than rape stem. Based on these results, radar chart was firstly applied to research the relationship of 10 elements in rape honey and its corresponding rape flower and stem. The aim of the present work was to study the possibility of using trace elements contents in rape flower to trace the geographical and botanical origin of honey instead of rape honey. It can be found from the radar charts that the stars of rape honey, rape flower and rape stem were similar to each other. This research not only provides the basic data of trace elements in comparative study of rape honey, but also gives scientific basis for tracing the origin of rape honey according to the trace elements in corresponding rape flower that replaces those of rape honey.

  9. [Application of ICP-MS to detection of mineral elements in double-low and double-high rapeseed].

    PubMed

    Zou, Juan; Lu, Jian-wei; Chen, Fang; Li, Yin-shui

    2009-09-01

    The object of the present study was to investigate ten necessary mineral elements in different varieties of rapeseed by ICP-MS. Thirty three samples of double-low (low in both glucosinolates and erucic acid) rapeseed (DLR) and 12 samples of double-high rapeseed (DHR) in the Yangtze River Valley were collected. The results showed that rapeseed contained many kinds of necessary elements, and there was a difference between DLR and DHR The average concentrations of P, K, Ca, Mg, S, Fe, Mn, Cu, Zn and B in DLR were 6.26 mg x g(-1), 10.17 mg x g(-1), 6.75 mg x g(-1), 4.82 mg x g(-1), 4.52 mg x g(-1), 96.20 microg x g(-1), 37.10 microg x g(-1), 3.84 microg x g(-1), 41.61 microg x g(-1) and 12.16 microg x g(-1), respectively, while for the mineral elements in DHR, the average values were 5.97 mg x g(-1), 10. 14 mg x g(-1), 6.31 mg x g(-1), 4.50 mg x g(-1), 9.06 mg x g(-1), 77.03 microg x g(-1), 49.86 microg x g(-1), 3.72 microg x g(-1), 40.58 microg x g(-1) and 11.79 microg x g(-1). The contents of most elements in DLR were higher than those in DHR, such as P, K, Ca, Mg, Fe, Cu, Zn and B. Furthermore, the differences in Ca, Mg and Fe contents between the two varieties were significant. It was concluded that the difference in concentrations of mineral elements can be regarded as a necessary factor for popularizing double-low rapeseed in the Yangtze River Valley.

  10. Impact history of the Chelyabinsk meteorite: Electron microprobe and LA-ICP-MS study of sulfides and metals

    NASA Astrophysics Data System (ADS)

    Andronikov, A. V.; Andronikova, I. E.; Hill, D. H.

    2015-12-01

    Electron microprobe and LA-ICP-MS study of sulfides and metals from two fragments of the LL5 Chelyabinsk meteorite were conducted. The fragments are impact breccias, one fragment contains both chondritic and shock vein lithologies, and the other contains shock-darkened chondritic clasts and vesicular impact melts. The chondritic lithology and shock veins display very similar opaque mineral compositions. The mineral compositions in the impact-melt breccias are distinctly different. The brecciated state of the Chelyabinsk meteorite suggests strong involvement of shock-related processes during the evolution of the parent body. Multiple heavy impact events occurred on the parent asteroid and on the Chelyabinsk meteoroid itself over the time period from ca. 4.5 Ga until ca. 1.2 Ma. The shock veins were produced in situ on the parent body. The impact-melt breccias could have formed because of the dramatic impact to the parent LL-chondrite body that could be partly disintegrated. The fragment containing shock-darkened chondritic clasts and vesicular impact melt lithologies preserves a record of melting, volatilization, partial degassing, and quenching of the molten material. The abundance and size (up to 1 mm) of the vesicles suggest that the impact melt must have been buried at some depth after formation. After impact and subsequent melting occurred, the impact-induced pressure on the shallow asteroid interior was released that caused "boiling" of volatiles and generation of S-rich bubbles. Such an impact excavated down to depths of the body generating multiple fragments with complicated histories. These fragments reaccumulated into a gravitational aggregate and formed the parental meteoroid for the Chelyabinsk meteorite.

  11. Arsenic speciation in environmental waters by a new specific phosphine modified polymer microsphere preconcentration and HPLC-ICP-MS determination.

    PubMed

    Jia, Xiaoyu; Gong, Dirong; Wang, Jiani; Huang, Fuyi; Duan, Taicheng; Zhang, Xian

    2016-11-01

    A new specific phosphine modified polymer microsphere (PPMs) was designed and used as the core adsorbent to comprehensively enrich both inorganic and organic arsenic species in environmental waters by on line solid-phase extraction (SPE). Avoiding any redox reagent, all the four arsenic species have been quantitatively retained on the home made mini-column with large number of positively charged adsorption groups, and then eluted rapidly (within seconds) with a mixed solution of ammonium nitrate and ammonium dihydrogen phosphate. The trace separation and determination of As(III), DMA, MMA and As(V) species have been simultaneously achieved by high performance liquid chromatography hyphenated to inductively coupled plasma spectrometry (HPLC-ICP-MS) technique. This work has developed a versatile tri-n-butylphosphine functionalized polymer microsphere for an efficient and reliable on-line of simultaneous preconcentration and detection of inorganic and organic arsenic speciation. Under the optimized experimental conditions, the enrichment factors obtained for As(III) and DMA with 25mL sample solution were 28, while for MMA and As(V) reached 30. The low detection limits of 1.2ngL(-1), 0.96ngL(-1), 0.82ngL(-1) and 0.91ngL(-1), with the relative standard deviations (RSDs) of 3.9%, 5.6%, 3.2% and 4.5% were obtained for As(III), DMA, MMA and As(V), respectively. The developed method was validated by analyzing Certified Reference Materials GSBZ 07-3171-2014, promising for routine monitoring of arsenic species in lake water, river water and seawater samples. PMID:27591635

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

    PubMed

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

    2016-07-01

    Nanoparticles (NPs) entering water systems are an emerging concern as NPs are more frequently manufactured and used. Single particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) methods were validated to detect Zn- and Ce-containing NPs in surface and drinking water using a short dwell time of 0.1 ms or lower, ensuring precision in single particle detection while eliminating the need for sample preparation. Using this technique, information regarding NP size, size distribution, particle concentration, and dissolved ion concentrations was obtained simultaneously. The fates of Zn- and Ce-NPs, including those found in river water and added engineered NPs, were evaluated by simulating a typical drinking water treatment process. Lime softening, alum coagulation, powdered activated carbon sorption, and disinfection by free chlorine were simulated sequentially using river water. Lime softening removed 38-53 % of Zn-containing and ZnO NPs and >99 % of Ce-containing and CeO2 NPs. Zn-containing and ZnO NP removal increased to 61-74 % and 77-79 % after alum coagulation and disinfection, respectively. Source and drinking water samples were collected from three large drinking water treatment facilities and analyzed for Zn- and Ce-containing NPs. Each facility had these types of NPs present. In all cases, particle concentrations were reduced by a minimum of 60 % and most were reduced by >95 % from source water to finished drinking water. This study concludes that uncoated ZnO and CeO2 NPs may be effectively removed by conventional drinking water treatments including lime softening and alum coagulation. PMID:26960902

  13. Simultaneous determination of organotin pesticides by HPLC-ICP-MS and their sorption, desorption, and transformation in freshwater sediments.

    PubMed

    Gui, Wenjun; Tian, Chunxia; Sun, Qianqian; Li, Shuying; Zhang, Wei; Tang, Jun; Zhu, Guonian

    2016-05-15

    In order to better assess their environmental risks, the sorption and degradation of triphenyltin hydroxide, azocyclotin and fenbutatin oxide were studied in two sediments under varying laboratory conditions in this study. An analytical method for simultaneous determination of the three organotins in environmental samples was firstly developed using high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). The limit of detection and limit of quantification for standards ranged from 0.13 to 1.46 μg/L. Fortification study showed that when spiked at 2-250 μg/kg the mass recoveries were 73.7-119.6%. Sorption isotherm experiments indicated that the organotins could be strongly adsorbed by the sediments, and organotin sorption kinetics obeyed the pseudo second-order kinetic model. The sorption affinity was inversely related to their water solubility. All isotherms fitted with the Henry mode fairly well (r(2) > 0.96) with distribution coefficients (Kd) ranging from 746.1 to 2465.2 mL/g. The three organotins could rapidly move from the upper water layer to the lower sediment layer, and they were all of moderate degradation compounds with the degradation half lives varying from 38.3 to 84.5d in anaerobic and aerobic water-sediment systems. The degradation rate seemed to be positively related to organic matter content of sediment. Result inferred that the three organotins had the low risks to pollute groundwater when applied on dry land and could moderately degrade in water-sediment system. However, more attention should still be paid to these organotins due to the wide application on agricultural field. PMID:26994697

  14. Comparative study on macro- and micro-elements concentration in Nicotiana tabacum and Faba siliquis plants by ICP-MS

    NASA Astrophysics Data System (ADS)

    Balazs, Zoltan; Voica, Cezara; Dehelean, Adriana; Magdas, Dana Alina; Ristoiu, Dumitru

    2015-12-01

    Plants are important components of ecosystems as they transfer elements from abiotic into biotic environments. The concentration of macro and micro-elements in tobacco leaves (Nicotiana tabacum) and bean (Faba siliquis) was analyzed using ICP-MS technique. The results obtained indicated that the mean concentration of Mg, P, K and Ca in tobacco leaves was 0.965, 0.812, 4.412 and 2.694 g.kg-1, respectively, while in bean samples were 0.899, 2.024, 6.725 and 1.387 g.kg-1, respectively. Mn concentration ranged from 156.835 mg.kg-1 to 234.593 mg.kg-1 in tobacco leaves and from 116.174 mg.kg-1 to 440.423 mg.kg-1 in bean samples. The results for Cu and Zn were between 7.262 mg.kg-1 and 105.738 mg.kg-1, 68.549 mg.kg-1 and 113.720 mg.kg-1 (tobacco leaves); and 6.830 mg.kg-1 and 46.034 mg.kg-1, 50.166 mg.kg-1 and 77.242 mg.kg-1 (bean samples), respectively. In analyzed samples, Pb, Cd and As concentrations ranged between <0.001-0.717 mg.kg-1, 0.046 mg.kg-1 -6.218 mg.kg-1, <0.001-0.381 mg.kg-1. The paper discusses the transfer of metal ions (Mn, As, Cd, Cu, Pb and Zn, respectively) from soil to these plants in terms of transfer factors (TF).

  15. A PIXE and ICP-MS analysis of metallic atmospheric contaminants in tree bark tissues, a basis for biomonitoring uses.

    PubMed

    Ayrault, Sophie; El Alaoui-Faris, Fatima Ezzahra; Asta, Juliette; Tissut, Michel; Daudin, Laurent; Mariet, Clarisse; Ravanel, Patrick; Gaudry, André; Cherkaoui, Rajaa

    2007-05-01

    The qualitative and quantitative metallic content of tree barks of Argania spinosa (L.) Skeels were studied. Argania spinosa is an endemic species in Morocco. This tree is adapted to semi-arid climates and exposed to specific conditions of relative humidity, temperature, wind, and particle transport. Three sites were sampled in Morocco: the large town of Rabat, the harbor of Agadir, and Aït Baha, a countryside location exposed to continuous desert wind. The methodologies included (1) in situ microanalysis with proton-induced X-ray emission (PIXE) and (2) trace element determinations by mass spectrometry with inductively coupled plasma (ICP-MS) associated with extraction procedures. Both methods allowed detection of elements coming from different bark compartments. The profile of airborne contaminants in the barks was typical of the sampling sites. The level of lead in barks sampled in Rabat reached 100 ng cm(-2), or higher, while it varied between 3 and 35 ng cm(-2) in Aït Baha. The in situ study of the microscopic structure of the bark provided the location of major and minor elements at various depths inside the bark. A differential between free deposit on the bark surface and penetrated content was found for the major and trace elements. The free deposit on the bark surface was suspected to be mostly the result of recent contamination. Part of the contaminants spread out on the surface penetrated the superficial suber. This long-term accumulation affected mostly Pb. In deeper levels, airborne elements at low concentrations and elements resulting from root uptake were concurrently present and resulted in a complex situation, as noted for zinc. PMID:17613745

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

    PubMed

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

    2016-07-01

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

  17. A method for the routine determination of methylmercury in marine tissue by GC isotope dilution-ICP-MS.

    PubMed

    Valdersnes, Stig; Maage, Amund; Fliegel, Daniel; Julshamn, Kåre

    2012-01-01

    Currently, there is no legal limit for methyl mercury (MeHg) in food; thus, no standardized method for the determination of MeHg in seafood exists within the European jurisdiction. In anticipation of a future legislative limit an inductively coupled plasma isotope dilution mass spectrometry (GC-ICP-ID-MS) method was developed in collaboration with the European Standardization Organization (CEN). The method comprises spiking the tissue sample with Me201Hg, followed by decomposition with tetramethylammonium hydroxide, pH adjustment and derivatization with sodium tetraethylborate, and finally organic extraction of the derivatized MeHg in a hexane phase. Subsequently, the sample is analyzed via GC-ICP-MS and the result calculated using the ID equation. The working range of the method was 0.0005-1.321 mg/kg MeHg in marine tissue, with an internal reproducibility (RSD) of 12-1%. The method was validated based on statistical measures, such as the z-scores, using the commercially available reference materials from National Institute of Standards and Technology Standard Reference Material (NIST SRM) 1566b, NIST SRM 2977 and National Research Council of Canada (NRCC) TORT 2, NRCC, DORM 3, NRCC DOLT 4, and European Reference Material (ERM) CE 464. Z-scores for all standard reference materials, except for NIST SRM 1566b, were better than 11.51. The wide range of marine tissues used during the validation ensures that the method will be applicable for measuring of MeHg in seafood matrixes of all kinds.

  18. U-Th dating of vein calcite by LA-MC-ICP-MS: preliminary results from geothermal systems

    NASA Astrophysics Data System (ADS)

    McGee, L. E.; Reich, M.; Rodriguez, V.; Leisen, M.; Barra, F.

    2014-12-01

    The measurement of U-series isotopes in precipitated minerals such as calcite holds various challenges, including low U and Th concentrations (in the ppb-ppt range), and the presence of detrital 232Th which can lead to age overestimations. Additionally, as yet there does not exist a calcite standard reference material for inter-laboratory accuracy and precision comparison, with most laboratories using their own in-house standard material and focussing largely on application to paleoclimate studies (e.g. corals and speleothems). In actively deforming regions, high-pressure hydrothermal fluids play an important role in faulting and vein formation, and commonly fault rupture is followed by rapid sealing through mineral precipitation. Therefore, precise dating of vein growth is of special importance to our understanding of the complex interplay between seismic events and fluid flow in the upper crust, and opens up a new field of study using U-Th techniques. The ability to accurately date fault-filling calcite within such settings has the power to elucidate the connection between structure and fluid flow in the development of geothermal systems, and provide valuable information on the longevity of the heat/water source, in addition to regional magmatic history. We are developing U-Th measurements and ages of vein calcite from geothermal systems using a Neptune Plus MC-ICP-MS (with 5 CDDs and 3 SEMs) coupled to an excimer 193nm Photon Machines laser. We will be comparing our results with an 189ka in-house flowstone calcite standard previously dated by TIMS, as well as developing a geothermal calcite standard.

  19. The Precise Determination of Cd Isotope Ratio in Geological Samples by MC-ICP-MS with Ion Exchange Separation

    NASA Astrophysics Data System (ADS)

    Du, C.; Hu, S.; Wang, D.; Jin, L.; Guo, W.

    2014-12-01

    Cadmium (Cd) is a trace element which occurs at μg g-1 level abundances in the crust. Cd isotopes have great prospects in the study of the cosmogony, the trace of anthropogenic sources, the micronutrient cycling and the ocean productivity. This study develops an optimized technique for the precise and accurate determination of Cd isotopic compositions. Cd was separated from the matrix by elution with AG-MP-1 anionic exchange chromatographic resin. The matrix elements (K, Na, Ca, Al, Fe, and Mg etc.), polyatomic interfered elements (Ge, Ga, Zr, Nb, Ru, and Mo), and isobaric interfered elements (In, Pd and most of Sn) were eluted using HCl with gradient descent concentrations (2, 0.3, 0.06, 0.012 and 0.0012 mol L-1). The same elution procedure was repeated to eliminate the residuel Sn (Sn/Cd < 0.018). The collected Cd was analyzed using MC-ICP-MS, in which the instrumental mass fractionation was controlled by a "sample-standard bracketing" technique. The recovery of Cd larger than 96.85%, and the δ114/110Cd are in the range of -1.43~+0.20‰ for ten geological reference materials (GSD-3a, GSD-5a, GSD-7a, GSD-6, GSD-9, GSD-10, GSD-11, GSD-12, GSD-23, and GSS-1). The δ114/110Cd obtained for GSS-1 soil sample relative to the NIST SRM 3108 Cd solution was 0.20, which was coherent with the literature values (0.08±0.23). This method had a precision of 0.001~0.002% (RSD), an error range of 0.06~0.14 (δ114/110Cd, 2σ), and a long-term reproducibility of 0.12 (δ114/110Cd, 2σ).

  20. Lead Isotope Measurement by Lead Double Spike and Thallium Spike Using MC-ICP-MS and TIMS - a Comparison Using Basaltic Samples

    NASA Astrophysics Data System (ADS)

    Taylor, R. N.; Ishizuka, O.

    2001-12-01

    Multi-collector ICP-MS has provided a new level of precision to lead isotope analysis using Thallium addition as an internal mass bias monitor. Further enhancement of precision has been achieved by the application of double lead spike to measurement procedures. In this study, we directly compare results using thallium addition and the new SBL74 double lead spike on both TIMS and MC-ICP-MS (Micromass IsoProbe). The comparisons are performed using standard Pb solutions and basaltic matrix-bearing solutions. Analyses of standards measured over 8 analytical sessions using the thallium spike method are reproducible to within 100 ppm for 206Pb/204Pb, 130 ppm for 207Pb/204Pb and 220 ppm (2sd) for 208Pb/204Pb. If the ratios for individual analytical sessions are normalised to the SRM981{day average}/SRM981true the increasing error with greater mass difference of the ratio is eliminated and all ratios are less than ±85 ppm. This implies that variability between the Tl and Pb mass bias factors on a day-to-day basis is the cause of increasing imprecision with mass difference. Double spike MC-ICP-MS is found to produce similar levels of precision to the Tl method for standards. However, the decreasing precision with increasing mass difference is greatly reduced, indicating that the correlation is due to Tl and Pb differences. With basaltic matrix samples with a single anion exchange separation, the effects of Tl-Pb differential mass bias are slightly exaggerated. We present the results from mixtures of SRM981 with Pb-free Fe measured using MC-ICP-MS using Tl and double spike mass bias correction, to replicate the basaltic matrix analyses.

  1. Selective hydride generation- cryotrapping- ICP-MS for arsenic speciation analysis at picogram levels: analysis of river and sea water reference materials and human bladder epithelial cells

    PubMed Central

    Matoušek, Tomáš; Currier, Jenna M.; Trojánková, Nikola; Saunders, R. Jesse; Ishida, María C.; González-Horta, Carmen; Musil, Stanislav; Mester, Zoltán; Stýblo, Miroslav; Dědina, Jiří

    2013-01-01

    An ultra sensitive method for arsenic (As) speciation analysis based on selective hydride generation (HG) with preconcentration by cryotrapping (CT) and inductively coupled plasma- mass spectrometry (ICP-MS) detection is presented. Determination of valence of the As species is performed by selective HG without prereduction (trivalent species only) or with L-cysteine prereduction (sum of tri- and pentavalent species). Methylated species are resolved on the basis of thermal desorption of formed methyl substituted arsines after collection at −196°C. Limits of detection of 3.4, 0.04, 0.14 and 0.10 pg mL−1 (ppt) were achieved for inorganic As, mono-, di- and trimethylated species, respectively, from a 500 μL sample. Speciation analysis of river water (NRC SLRS-4 and SLRS-5) and sea water (NRC CASS-4, CASS-5 and NASS-5) reference materials certified to contain 0.4 to 1.3 ng mL−1 total As was performed. The concentrations of methylated As species in tens of pg mL−1 range obtained by HG-CT-ICP-MS systems in three laboratories were in excellent agreement and compared well with results of HG-CT-atomic absorption spectrometry and anion exchange liquid chromatography- ICP-MS; sums of detected species agreed well with the certified total As content. HG-CT-ICP-MS method was successfully used for analysis of microsamples of exfoliated bladder epithelial cells isolated from human urine. Here, samples of lysates of 25 to 550 thousand cells contained typically tens pg up to ng of iAs species and from single to hundreds pg of methylated species, well within detection power of the presented method. A significant portion of As in the cells was found in the form of the highly toxic trivalent species. PMID:24014931

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

    PubMed Central

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

    2015-01-01

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

  3. Combined apatite fission track and U-Pb dating by LA-ICPMS

    NASA Astrophysics Data System (ADS)

    Chew, D. M.; Donelick, R. A.

    2012-04-01

    fractionation are challenges in apatite U-Pb dating by LA-ICPMS. Isochron-based approaches to common Pb correction require a significant spread in common Pb / radiogenic Pb ratios. This is not usually possible on individual detrital apatite grains and hence the 204Pb-, 207Pb- and 208Pb-correction methods are preferred. Uranium concentration measurements by ICPMS employ large peak jumps (the internal standard is a Ca isotope) which require a quadrupole or a rapid-scanning magnetic-sector LA-ICPMS system. These single-collector instruments require a prohibitively long dwell time on the low intensity 204Pb peak to measure it accurately and hence the 207Pb- and 208Pb-correction methods are preferred. Uranium-concentration measurements in fission-track dating require well-constrained ablation depths during analysis and hence spot analyses are preferred to rastering. Laser-induced U-Pb fractionation is corrected for by sample-standard bracketing using a variety of apatite standards (Durango, Emerald Lake, Fish Canyon Tuff, Kovdor, Otter Lake and McClure Mountain syenite). Of these, Emerald Lake (Chew et al., 2011) and McClure Mountain syenite apatite are recommended as primary standards with Durango apatite making a suitable secondary standard. Offline data-reduction uses custom-written software for ICPMS data processing (the UPbICP package of Ray Donelick) or the freeware IOLITE data-reduction package of Paton et al. (2010).

  4. Use of the bromine isotope ratio in HPLC-ICP-MS and HPLC-ESI-MS analysis of a new drug in development.

    PubMed

    Cuyckens, Filip; Balcaen, Lieve I L; De Wolf, Kenny; De Samber, Bjorn; Van Looveren, Cis; Hurkmans, Rob; Vanhaecke, Frank

    2008-04-01

    A combination of inductively coupled plasma mass spectrometry (ICP-MS) and electrospray ionization mass spectrometry (ESI-MS) was deployed for the metabolite profiling and metabolite identification of a new antituberculosis compound (R207910, also known as TMC207) that is currently in drug development. R207910 contains one bromine atom, allowing the detection by ICP-MS. Fluctuations in the Br sensitivity caused by the HPLC gradient were counteracted by the use of species-unspecific isotope dilution. In order to evaluate the method developed, the results obtained were compared with those acquired via radioactivity detection. HPLC-ESI-MS was used for the structural identification of R207910 and its metabolites. The (79)Br/(81)Br isotope ratio is also valuable in the search for metabolites in the complex background of endogenous compounds obtained using HPLC-ESI-MS analyses. Data-dependent scanning using isotope recognition with an ion trap mass spectrometer or processing of Q-Tof data provides HPLC-ICP-MS-like "bromatograms". The combination of accurate mass measurements and the fragmentation behavior in the MS(2) spectra obtained using the Q-Tof Ultima mass spectrometer or MS(n) spectra acquired using the LTQ-Orbitrap allowed structural characterization of the main metabolites of R207910 in methanolic dog and rat faeces extracts taken 0-24 h post-dose.

  5. Combined use of HPLC-ICP-MS and microwave-assisted extraction for the determination of cobalt compounds in nutritive supplements.

    PubMed

    Yang, Fang-Yu; Jiang, Shiuh-Jen; Sahayam, A C

    2014-03-15

    Speciation analysis of cobalt in nutritive supplements has been carried out using HPLC and ICP-MS equipped with a membrane desolvation sample introduction system as detector. In this study, cobalt containing compounds, namely Co(II), cyanocobalamin (CN-Cbl) and hydroxylcobalamin (OH-Cbl), were well separated by reversed phase HPLC with a C8-HPLC column as the stationary phase and 8 mmol L(-1) ammonium acetate in 22%v/v methanol solution (pH 4) as the mobile phase using isocratic elution. Detection limit was in the range of 0.008-0.014 μg CoL(-1) for various Co species. Over 98% of the total cobalt species was extracted in nutritive supplements using a 0.5%v/v HNO3 solution in a microwave field; and the spike recovery was in the range of 92-108% for various species. The HPLC-ICP-MS results showed a satisfactory agreement with the total cobalt concentrations obtained by ICP-MS analysis of completely dissolved samples.

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

    USGS Publications Warehouse

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

    2012-01-01

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

  7. Selenium transformation studies during broccoli (Brassica oleracea) growing process by liquid chromatography-inductively coupled plasma mass spectrometry (LC-ICP-MS).

    PubMed

    Pedrero, Zoyne; Elvira, Daniel; Cámara, Carmen; Madrid, Yolanda

    2007-07-23

    Selenium uptake and transformation was studied in Se-enriched Broccoli (Brassica olearacea). Plants were grown in hydroponic culture and exposed during 40 days to Na2SeO3 (1 mg L(-1)). After growing, the plants were harvested and their different parts (roots, stems and fruit) were analyzed by ICP-MS or LC-ICP-MS. Se-species were identified and quantified after enzymatic extraction by using both an anion exchange (PRP-X100), and a size exclusion/ion exchange (Shodex Asahipak) chromatographic columns. Selenium translocation and transformation Se species in plants was studied through the Se-speciation in root, stem and fruit. After 40 days of exposure, selenomethionine was the major species found in roots, however, Se-methylselenocysteine was the main species found in the fruit, suggesting Broccoli as a source of this important selenoamino acid in human diet. However, the degree of meal processing influences the stability of Se-aminoacids. Speciation studies in boiled Broccoli and in the extraction water were also carried out. This experiment revealed a noticeable degradation of Se-methylselenocysteine in the boiled Broccoli fruit. Proteins soluble in Tris-HCl were analyzed by two-dimensional chromatography coupled to ICP-MS. The results obtained contribute not only to a deeper understanding of Se accumulation mechanisms by plants but also to further functional food complements preparation and the effect of food processing on species stability.

  8. Analysis of twenty five impurities in uranium matrix by ICP-MS with iron measurement optimized by using reaction collision cell, cold plasma or medium resolution.

    PubMed

    Quemet, Alexandre; Brennetot, Rene; Chevalier, Emilie; Prian, Edwina; Laridon, Anne-Laure; Mariet, Clarisse; Fichet, Pascal; Laszak, Ivan; Goutelard, Florence

    2012-09-15

    An analytical procedure was developed to determine the concentration of 25 impurities (Li, Be, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ag, Cd, In, Sm, Eu, Gd, Dy, W, Pb, Bi and Th) in a uranium matrix using the quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS). The dissolution of U(3)O(8) powder was made with a mixture of hydrochloric acid and nitric acid. Then, a selective separation of uranium using the UTEVA column was used before measurement by Q-ICP-MS. The procedure developed was verified using the Certified Reference Material "Morille". The analytical results agree well except for 5 elements where values are underestimated (Li, Be, In, Pb and Bi). Among the list of impurities, iron was particularly investigated because it is well known that this element possesses a polyatomic interference that increases the detection limit. A comparison between iron detection limits obtained with different methods was performed. Iron polyatomic interference was at least reduced, or at best entirely resolved in some cases, by using the cold plasma or the collision/reaction cell with several gases (He, NH(3) and CH(4)). High-resolution ICP-MS was used to compare the results obtained. A detection limit as low as 8 ng L(-1) was achieved. PMID:22967543

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

    PubMed

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

    2014-10-15

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

  10. Enhanced detection of DNA sequences using end-point PCR amplification and online gel electrophoresis (GE)-ICP-MS: determination of gene copy number variations.

    PubMed

    González, T Iglesias; Espina, M; Sierra, L M; Bettmer, J; Blanco-González, E; Montes-Bayón, M; Sanz-Medel, A

    2014-11-18

    The design and evaluation of analytical methods that permit quantitative analysis of specific DNA sequences is exponentially increasing. For this purpose, highly sensitive methodologies usually based on labeling protocols with fluorescent dyes or nanoparticles are often explored. Here, the possibility of label-free signal amplification using end-point polymerase chain reaction (PCR) are exploited using on-column agarose gel electrophoresis as separation and inductively coupled plasma-mass spectrometry (ICP-MS) for the detection of phosphorus in amplified DNA sequences. The calibration of the separation system with a DNA ladder permits direct estimation of the size of the amplified gene fragment after PCR. With this knowledge, and considering the compound-independent quantification capabilities exhibited by ICP-MS for phosphorus (it is only dependent on the number of P atoms per molecule), the correlation of the P-peak area of the amplified gene fragment, with respect to the gene copy numbers (in the starting DNA), is then established. Such a relationship would permit the determination of copy number variations (CNVs) in genomic DNA using ICP-MS measurements. The method detection limit, in terms of the required amount of starting DNA, is ∼6 ng (or 1000 cells if 100% extraction efficiency is expected). The suitability of the proposed label-free amplification strategy is applied to CNVs monitoring in cells exposed to a chemical agent capable of deletion induction, such as cisplatin. PMID:25312744

  11. High temperature liquid chromatography hyphenated with ESI-MS and ICP-MS detection for the structural characterization and quantification of halogen containing drug metabolites.

    PubMed

    de Vlieger, Jon S B; Giezen, Mark J N; Falck, David; Tump, Cornelis; van Heuveln, Fred; Giera, Martin; Kool, Jeroen; Lingeman, Henk; Wieling, Jaap; Honing, Maarten; Irth, Hubertus; Niessen, Wilfried M A

    2011-07-18

    In this paper we describe the hyphenation of high temperature liquid chromatography with ICP-MS and ESI-MS for the characterization of halogen containing drug metabolites. The use of temperature gradients up to 200°C enabled the separation of metabolites with low organic modifier content. This specific property allowed the use of detection methods that suffer from (significant) changes in analyte response factors as a function of the organic modifier content such as ICP-MS. Metabolites of two kinase inhibitors (SB-203580-Iodo and MAPK inhibitor VIII) produced by bacterial cytochrome P450 BM3 mutants and human liver microsomes were identified based on high resolution MS(n) data. Quantification was done using their normalized and elemental specific response in the ICP-MS. The importance of these kinds of quantification strategies is stressed by the observation that the difference of the position of one oxygen atom in a structure can greatly affect its response in ESI-MS and UV detection.

  12. Evaluating the provenance of Permian-Triassic and Palaeocene-Eocene ash beds by high precision U-Pb and Lu-Hf isotopic analyses of zircons: linking local sedimentary records to global events

    NASA Astrophysics Data System (ADS)

    Eivind Augland, Lars; Jones, Morgan; Planke, Sverre; Svensen, Henrik; Tegner, Christian

    2016-04-01

    Zircons are a powerful tool in geochronology and isotope geochemistry, as their affinity for U and Hf in the crystal structure and the low initial Pb and Lu allow for precise and accurate dating by U-Pb ID-TIMS and precise and accurate determination of initial Hf isotopic composition by solution MC-ICP-MS analysis. The U-Pb analyses provide accurate chronostratigraphic controls on the sedimentary successions and absolute age frames for the biotic evolution across geological boundaries. Moreover, the analyses of Lu-Hf by solution MC-ICP-MS after Hf-purification column chemistry provide a powerful and robust fingerprinting tool to test the provenance of individual ash beds. Here we focus on ash beds from Permian-Triassic and Palaeocene successions in Svalbard and from the Palaeocene-Eocene Thermal Maximum (PETM) in Fur, Denmark. Used in combination with whole rock geochemistry from the ash layers and the available geochemical and isotopic data from potential source volcanoes, these data are used to evaluate the provenance of the Permian-Triassic and Palaeocene ashes preserved in Svalbard and PETM ashes in Denmark. If explosive eruptions from volcanic centres such as the Siberian Traps and the North Atlantic Igneous Province (NAIP) can be traced to distal basins as ash layers, they provide robust tests of hypotheses of global synchronicity of environmental changes and biotic crises. In addition, the potential correlation of ash layers with source volcanoes will aid in constraining the extent of explosive volcanism in the respective volcanic centres. The new integrated data sets will also contribute to establish new reference sections for the study of these boundary events when combined with stable isotope data and biostratigraphy.

  13. Combining fs LA-ICP-MS, FIB and STXM-NEXAFS Methods for in-situ High-Spatial-Resolution Rock Varnish Analyses at the nm to µm Scale

    NASA Astrophysics Data System (ADS)

    Macholdt, D.; Andreae, M. O.; Jochum, K. P.; Kappl, M.; Kilcoyne, A. L. D.; Müller, M.; Pöhlker, C.; Stoll, B.; Weber, B.; Weigand, M.; Weis, U.

    2014-12-01

    Since over 200 years a number of studies debate the origin of the black or red, up to 250 µm thick coatings on desert rocks, referred to as rock varnish. The main components of varnish are poorly crystallized Mn and Fe oxides and clay minerals. Both biological and geological processes have been suggested for the genesis. We used a combination of 200 nm-femtosecond LA-ICP-MS, focused ion beam (FIB) slicing and scanning transmission X-ray microscopy - near edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS) for the high-spatial-resolution analysis of rock varnish from different locations (Negev, Israel; Knersvlakte, South Africa; Death Valley and Mojave Desert, California). Femtosecond LA-ICP-MS was used for the quantitative determination of major and trace element concentrations. In-situ measurements were conducted on thick sections with the advantages of non-matrix matched calibration, low ablation depth of ~10 µm for laser spot sizes of 10-40 µm and low detection limits of trace elements (< 0.01 - 1 µg g-1). Our results demonstrate that elements, such as Mn, Co, Pb, Ni and Cu, are highly enriched in varnish relative to the upper continental crust (up to a factor of 1000). Differences between varnishes from the various locations can be observed especially for the Mn/Fe (0.4-25.6), Mn/Ba (3-363) and Ni/Co (0.03-1.8) ratios. The REE patterns differ with LaN/YbN = 2-14 and positive Ce anomalies (Ce/Ce* = 1.1 - 9.1). To study the internal structures of varnish, 100 - 200 nm thick FIB slices were prepared to perform mappings of Fe, Mn, O, N, CO3, K, Ca, and C at the nm scale. In addition, the oxidation stages of Mn and Fe were identified. Banded internal structures of Mn and organic C can be observed in some samples, and cavities that are partly filled by C and Mn rich material. Some coatings tend to incorporate bigger dust grains (> 1 µm), while others only show very fine grained material (< 0.1 µm). The results of the combined microanalytical

  14. MKED1: A new titanite standard for in situ microanalysis of trace elements, Sm-Nd isotopes, and U-Pb geochronology

    NASA Astrophysics Data System (ADS)

    Spandler, C.; Hammerli, J.; Hilbert-Wolf, H.; Sha, P.; Hu, Y.; Roberts, E.; Schmitz, M. D.

    2015-12-01

    Titanite has great potential as a petrogenetic indicator and mineral geochronometer as it can host high trace element concentrations and it occurs in a wide range of rock types. Here, we describe a potential new titanite standard for calibration of the chemical and isotopic composition of titanite of varying age and origin. Through comprehensive bulk analysis of mm-size crystal fragments and in-situ microanalysis, we show that the titanite, labeled MKED1, is largely free of inclusions and is homogenous at the level of analytical precision for major element, U-Pb isotope and Sm-Nd isotope composition. Some minor zoning in trace element composition is recognized using backscatter electron imaging, although the trace element concentrations of each of these zones are also very homogenous. MKED1 has high contents of REE, Th, U, and radiogenic Pb, but very low levels of common Pb. U-Pb isotope data (ID-TIMS and LA-ICP-MS) show MKED1 to be concordant with an age of ca. 1518 Ma. Cross calibration with other titanite standards demonstrates that MKED1 can be used as a primary standard for determining U-Pb ages of titanite ranging in age from Precambrian to Neogene. We also show that MKED1 is suitable as a Sm-Nd isotope standard due to its high REE concentrations and homogenous 147Sm/144Nd and 143Nd/144Nd content. We suggest MKED1 can be employed as a trace element, U-Pb isotope and Sm-Nd isotope standard for in situ or bulk analytical methods, including techniques that allow simultaneous collection of multiple elemental and/or isotopic data sets in situ. We present two case studies to demonstrate the potential of titanite analysis for resolving geological problems: The first examines the genesis of Cu-REE skarn mineralization from the Mt Isa Inlier, Australia, and the second study investigates the timing and origin of volcanism and sedimentation in the Western Branch of the East African Rift.

  15. Inductively Coupled Plasma: Fundamental Particle Investigations with Laser Ablation and Applications in Magnetic Sector Mass Spectrometry

    SciTech Connect

    Saetveit, Nathan Joe

    2008-01-01

    Particle size effects and elemental fractionation in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) are investigated with nanosecond and femtosecond laser ablation, differential mobility analysis, and magnetic sector ICP-MS. Laser pulse width was found to have a significant influence on the LA particle size distribution and the elemental composition of the aerosol and thus fractionation. Emission from individual particles from solution nebulization, glass, and a pressed powder pellet are observed with high speed digital photography. The presence of intact particles in an ICP is shown to be a likely source of fractionation. A technique for the online detection of stimulated elemental release from neural tissue using magnetic sector ICP-MS is described. Detection limits of 1 μg L-1 or better were found for P, Mn, Fe, Cu, and Zn in a 60 μL injection in a physiological saline matrix.

  16. U-Pb detrital zircon age patterns of Cenozoic clastic sedimentary rocks in Trinidad and its implications

    NASA Astrophysics Data System (ADS)

    Xie, Xiangyang; Mann, Paul

    2014-06-01

    The Cenozoic evolution of northern South America can be simplified as a diachronous, west-to-east change from north-facing passive margin, to active convergence and transcurrent plate margin. As the current eastern end of the Caribbean-South America plate boundary, the Trinidad area records the most recent tectonic regime transition. Documenting the provenance of Cenozoic clastic rocks in Trinidad provides insights into the spatial and temporal relationships between mountain range uplifting, sediment dispersal, and drainage system development along the eastern end of the Caribbean-South American plate boundary. Four Eocene to Pliocene age