Knowledge Base

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  • TIMS
  • Triton
  • Ca isotopes
  • Osteoporosis

A pilot study on the use of natural calcium isotope (44Ca/40Ca) fractionation in urine as a proxy for the human body calcium balance

Alexander Heuser (1,2), Anton Eisenhauer (2)

1) Leibniz-Institut für Meereswissenschaften, IFM-GEOMAR, Wischhofstr. 1-3, 24148 Kiel, Germany, 2) Steinmann Institut für Geologie, Mineralogie und Paläontologie, Universität Bonn, Poppelsdorfer Schloss, 53115 Bonn, Germany

Bone (2010), V46(4), pp889–896, doi: 10.1016/j.bone.2009.11.037

Goal: We explored the possibility of using natural calcium (Ca) isotope variations in the urine (δ44/40Ca urine) as a proxy for the Ca balance in the human body. We chose two test persons extremely different in their health status, gender and age (4-year-old healthy boy and a 60-year-old woman known to suffer from osteoporosis).

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  • TIMS
  • Triton Plus
  • Ca isotopes
  • Static Collection

TIMS measurements of full range of natural Ca isotopes withinternally consistent fractionation correction

Maria O. Naumenko-Dèzes (1), Claudia Bouman (2), Thomas F. Nägler (1) Klaus Mezger (1) and Igor M. Villa (1,3)

1) Institute für Geologie, Universität Bern, Baltzerstrasse 1+3, 3012 Bern, Switzerland, 2) Thermo Fisher Scientific, Hanna-Kunath-Strasse 11, 28199 Bremen, Germany, 3) Università di Milano Bicocca, Piazza della Scienza 4, 20126 Milano, Italy

International Journal of Mass Spectrometry (2015), V387, pp60-68, doi: 10.1016/j.ijms.2015.07.012

Goal: This study presents static measurements of the Ca isotopic composition of standard reference materials SRM 915 a/b on a Triton Plus thermal ionization mass spectrometer with a specially developed Faradaycup array allowing simultaneous measurement of 40Ca and 48Ca. The total amount of Ca in all analyses was kept <1 g. With this setup the measurement uncertainties were 0.06‰ for 40Ca/44Ca and 0.12‰ for 48Ca/40Ca. Measuring all isotopes simultaneously better allows to test the internal consistency of different Ca isotope abundances reported in the literature.

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  • Mass Spectrometry
  • Ca Isotopes
  • Fractionation

Calcium Isotope Analysis by Mass Spectrometry

Sergei F. Boulyga

Safeguards Analytical Laboratory, Department of Nuclear Sciences and Applications, International Atomic Energy Agency, Wagramer Strasse 5, 1400 Vienna, Austria

Mass Spectrometry Reviews (2010), V29, pp685– 716, doi:

Goal: The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades.

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  • TIMS
  • Triton: Ca isotopes
  • Meteorites

Calcium Isotope Composition of Meteorites, Earth, and Mars

Justin I. Simon (1), Donald J. DePaolo (1) and Frederic Moynier (2)

1) Center for Isotope Geochemistry, Earth and Planetary Science, University of California, Berkeley, CA 94720, USA, 2) Earth and Planetary Sciences and McDonnell Center for Space Sciences, Washington University in St Louis, MO 63130, USA

The Astrophysical Journal (2009), V702, pp707–715, doi: 10.1088/0004-637X/702/1/707

Goal: The relative abundances of calcium isotopes in the mass range 40–44 were measured in primitive and differentiated meteorites and igneous rocks from Earth and Mars in search of non-mass-dependent variations that could provide clues about early solar system processes. Most bulk samples of planetary materials have calcium isotopic compositions identical with Earth’s within the current resolution of about 0.01% in 40Ca/44Ca. Possible exceptions include carbonaceous chondrites, some ordinary chondrites, and two samples of calcium–aluminumrich inclusions, which have small excesses of 40Ca.

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  • MC-ICPMS
  • Neptune
  • Ca isotopes
  • Osteopenia

Rapidly assessing changes in bone mineral balance using natural stable calcium isotopes

Jennifer L. L. Morgan (1,3), Joseph L. Skulan (2), Gwyneth W. Gordon (2), Stephen J. Romaniello (2) Scott M. Smith (3) and Ariel D. Anbara (2)

1) Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, 85287, USA; 2) School of Earth and Space Exploration, Arizona State University, Tempe, AZ, 85287, USA; 3) Human Adaptation and Countermeasures Division, National Aeronautics and Space Administration, Houston, TX, 77058, USA

Proceedings of the National Academy of Science of the United States of America (2012), V109(25), pp9989–9994, doi:10.1073/pnas.1119587109

Goal: The ability to rapidly detect changes in bone mineral balance (BMB) would be of great value in the early diagnosis and evaluation of therapies for metabolic bone diseases such as osteoporosis and some cancers. However, measurements of BMB are hampered by difficulties with using biochemical markers to quantify the relative rates of bone resorption and formation and the need to wait months to years for altered BMB to produce changes in bone mineral density large enough to resolve by X-ray densitometry. We show here that, in humans, the natural abundances of Ca isotopes in urine change rapidly in response to changes in BMB. In a bed rest experiment, use of high-precision isotope ratio MS allowed the onset of bone loss to be detected in Ca isotope data after about 1 wk, long before bone mineral density has changed enough to be detectable with densitometry.

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  • MC-ICPMS
  • Neptune
  • Ca isotopes
  • Urine

High-Precision Measurement of Variations in Calcium Isotope Ratios in Urine by Multiple Collector Inductively Coupled Plasma Mass Spectrometry

Jennifer L. L. Morgan (1), Gwyneth W. Gordon (2), Ruth C. Arrua (2), Joseph L. Skulan (3), Ariel D. Anbar (1,2) Thomas D. Bullen (4)

1) Arizona State University, Department of Chemistry and Biochemistry, P.O. Box 871604, Tempe, Arizona 85287, United States, 2) Arizona State University, School of Earth and Space Exploration, P.O. Box 871404, Tempe, Arizona 85287, United States, 3) University of Wisconsin, Geology Museum, 1215 West Dayton Street, Madison, Wisconsin 53706, United States, 4) Water Resources Discipline, U.S. Geological Survey, 345 Middlefield Road, Menlo Park, California 94025, United States

Analytical Chemistry (2011), V83(18), pp6956-62, doi: 10.1021/ac200361t

Goal: We describe a new chemical separation method to isolate Ca from other matrix elements in biological samples, developed with the long-term goal of making highprecision measurement of natural stable Ca isotope variations a clinically applicable tool to assess bone mineral balance. A new two-column procedure utilizingHBr achieves the purity required to accurately and precisely measure two Ca isotope ratios (44Ca/42Ca and 44Ca/43Ca) on a Neptune multiple collector inductively coupled plasmamass spectrometer (MC-ICPMS) in urine.

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  • TIMS
  • Triton: Ca isotopes
  • Plants

Experimental identification of Ca isotopic fractionations in higher plants

Florian Cobert (1), Anne-Désirée Schmitt (2), Pascale Bourgeade (2), François Labolle (3), Pierre-Marie Badot (2), François Chabaux (1), Peter Stille (1)

1) Laboratoire d’Hydrologie et de Ge´ochimie de Strasbourg, Université de Strasbourg/EOST, CNRS, 1 rue Blessig, F-67000 Strasbourg, France, 2) Université de Franche-Comté et CNRS-UMR 6249, Chrono-environnement, 16, Route de Gray, 25030 Besanc on Cedex, France, 3) Université de Strasbourg, Institut de Zoologie et de Biologie générale, 12, rue de l’Université , 67000 Strasbourg, France

Geochimica et Cosmochimica Acta (2011), V75, pp5467–5482, doi: 10.1016/j.gca.2011.06.032

Goal: Hydroponic experiments have been performed in order to identify the co-occurring geochemical and biological processes affecting the Ca isotopic compositions within plants. To test the influence of the Ca concentration and pH of the nutritive solution on the Ca isotopic composition of the different plant organs, four experimental conditions were chosen combining two different Ca concentrations (5 and 60 ppm) and two pHs (4 and 6). The study was performed on rapid growing bean plants in order to have a complete growth cycle.

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  • MC-ICPMS
  • Neptune
  • Ca isotopes
  • Carbonates

Calcium-isotope fractionation in selected modern and ancient marine carbonates

Thomas Steuber (1,2) and Dieter Buhl (1)

1) Ruhr-Universität, Institut für Geologie, Mineralogie und Geophysik, 44801 Bochum, Germany, 2) The Petroleum Institute, P.O. Box 2533, Abu Dhabi, UAE.

Geochimica et Cosmochimica Acta (2006), V70, pp5507–5521, doi: 10.1016/j.gca.2006.08.028

Goal: The calcium-isotope composition (d44/42Ca) was analyzed in modern, Cretaceous and Carboniferous marine skeletal carbonates as well as in bioclasts, non-skeletal components, and diagenetic cements of Cretaceous and Carboniferous limestones. In order to gain insight in Ca2+ aq–CaCO3-isotope fractionation mechanisms in marine carbonates, splits of samples were analyzed for Sr, Mg, Fe, and Mn concentrations and for their oxygen and carbon isotopic composition.

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  • MC-ICPMS
  • Neptune
  • Ca isotopes
  • High Resolution

High precision calcium isotope ratio measurements using a magnetic sector multiple collector inductively coupled plasma mass spectrometer

Michael E. Wieser (1,3), Dieter Buhl (2), Claudia Bouman (1) and Johannes Schwieters (1)

1)Thermo Electron (Bremen) GmbH, Barkhausenstr. 2, 28197, Germany, 2) Institut für Geologie Mineralogie und Geohphysik, Ruhr Universität Bochum, Universitätsstr. 150, 44801, Germany, 3) University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada

Journal of Analytical Atomic Spectrometry (2004), V19, pp844-851, doi: 10.1039/b403339f

Goal: Calcium isotope abundances were measured using a Finnigan Neptune magnetic sector multiple collector inductively coupled plasma mass spectrometer capable of resolving all molecular isobaric interferences from 42Ca, 43Ca, 44Ca, 46Ca and 48Ca. Scattering events caused by the intense 40Ar+ ion beam did not contribute to the uncertainty in the baseline of the calcium mass spectrum. Quantitative separation of the calcium from the sample matrix was carried out to ensure that the measurements were independent of the sample type. In addition, thorough desolvation of the aerosol was found to have a significant effect on the stability and sensitivity of the method.

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  • n-TIMS
  • Triton Plus
  • Boron Isotopes

A high-throughput system for boron microsublimation and isotope analysis by total evaporation thermal ionization mass spectrometry

Yi-Wei Liu (1), Sarah M. Aciego (1), Alan D. Wanamaker Jr. (2) and Bryan K. Sell (1)

1) Earth and Environmental Sciences, University of Michigan, 1100 N. University Avenue, Ann Arbor, MI 48109, USA, 2) Department of Geological and Atmospheric Sciences, Iowa State University, Ames, IA 50011, USA

Rapid Communications in Mass Spectrometry (2013), V27, pp1705–1714, doi: 10.1002/rcm.6619

Goal: Research on the ocean carbon cycle is vitally important due to the projected impacts of atmospheric CO2 on global temperatures and climate change, but also on ocean chemistry. The direct influence of this CO2 rise on the seawater pH can be evaluated from the boron isotopic composition in biogenic carbonates; however, conscientious laboratory techniques and data treatment are vital in obtaining accurate and precise results. A rapid-throughput boron purification and Total Evaporation Thermal Ionization Mass Spectrometry method was developed for high accuracy and precision boron isotopic analysis for small (ng) sample sizes

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  • Positive TIMS
  • MC-ICPMS
  • B isotopes
  • Purification

An improved procedure for separation/purification of boron from complex matrices and high-precision measurement of boron isotopes by positive thermal ionization and multicollector inductively coupled plasma mass spectrometry

Hai-Zhen Wei (1), Shao-Yong Jiang (1,2), N. Gary Hemming (3,4), Jing-Hong Yang (1), Tao Yang (1), He-Pin Wu (1), Tang-Li Yang (1), Xiong Yan (1), Wei Pu (1)

1) State Key Laboratory for Mineral Deposits Research, Department of Earth Sciences, Nanjing University, Nanjing 210093, PR China, 2)State Key Laboratory of Geological Processes and Mineral Resources, Faculty of Earth Resources, China University of Geosciences, Wuhan, Hubei 430074, PR China, 3) Department of Earth and Environmental Sciences, Lamont-Doherty Earth Observatory of Columbia University, Palisades, NY 10964-8000, USA, 4) Queens College School of Earth and Environmental Sciences, Flushing, NY 11367, USA

Talanta (2014) , V123, pp151–160, doi: 10.1016/j.talanta.2014.02.009

Goal: In order to eliminate boron loss and potential isotopic fractionation during chemical pretreatment of natural samples with complex matrices, a three-column ion-exchange separation/purification procedure has been modified, which ensures more than 98% recovery of boron from each step for a wide range of sample matrices, and is applicable for boron isotope analysis by both TIMS and MC-ICP-MS.

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  • MC-ICPMS
  • Neptune
  • B isotopes
  • Laser Ablation

Determination of boron isotope compositions of geological materials by laser ablation MC-ICP-MS using newly designed high sensitivity skimmer and sample cones

Lin Lin (1), Zhaochu Hu (1a), Lu Yang (2), Wen Zhang (1), Yongsheng Liu (1), Shan Gao (1), Shenghong Hu (1)

1) State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, China, 2) Measurement Science and Standards, National Research Council Canada, Ottawa, Ontario K1A 0R6, Canada

Chemical Geology (2014), V386, pp22-30, doi: 10.1016/j.chemgeo.2014.08.001

Goal: The effects of addition of nitrogen gas with use of three different combinations of sample and skimmer cones on the performance of LA-MC-ICP-MS for in situ B isotope ratio measurements were investigated in detail.

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  • MC-ICPMS
  • Neptune
  • B isotopes
  • Direct Injection

A fully automated direct injection nebulizer (d-DIHEN) for MC-ICP-MS isotope analysis: application to boron isotope ratio measurements

Pascale Louvat, Julien Moureau, Guillaume Paris, Julien Bouchez, Johanna Noireaux and Jérôme Gaillardet

Institut de Physique du Globe de Paris, Sorbonne Paris Cité, Université Paris-Diderot, UMR CNRS 7154, 1 rue Jussieu, 75238, France

Journal of Analytical Atomic Spectrometry (2014), V29, pp1698-1707, doi: 10.1039/c4ja00098f

Goal: This work presents a fully automated setup for using direct injection nebulization as an introduction system for solution measurements by MC-ICP-MS, here applied to boron isotopes in pure boric acid solutions and natural samples. In this setup, a direct injection nebulizer (d-DIHEN) is plugged into the plasma torch without any spray chamber, and an automated 6-port valve interfaces the nebulizer and the autosampler. The advantages of a d-DIHEN for boron isotope ratio measurements are high sensitivity and short washout times, allowing for sample–standard bracketing (SSB) measurements at a higher rate than spray chambers.

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  • MC-ICPMS
  • Neptune
  • B isotopes
  • Marine Carbonates

Rapid, high-precision measurements of boron isotopic compositions in marine carbonates

Malcolm T. McCulloch (1,2), Michael Holcomb (1,2), Kai Rankenburg (2) and Julie A. Trotter (2)

1) The University of Western Australia, School of Earth and Environment and ARC Centre of Excellence in Coral Reef Studies, Crawley 6009, Western Australia, Australia, 2) The University of Western Australia, School of Earth and Environment and Oceans Institute, Crawley 6009, Western Australia, Australia

Rapid Communications in Mass Spectrometry (2014), v28, pp1–9, doi: 10.1002/rcm.7065

Goal: The isotopic composition and elemental abundance of boron (B) in marine carbonates provide a powerful tool for tracking changes in seawater pH and carbonate chemistry. Progress in this field has, however, been hampered by the volatile nature of B, its persistent memory, and other uncertainties associated with conventional chemical extraction and mass spectrometric measurements. Here we show that for marine carbonates, these limitations can be overcome by using a simplified, low-blank, chemical extraction technique combined with robust multi-collector inductively couple plasma mass spectrometry (MC-ICPMS) methods.

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  • TIMS
  • (MC-)ICPMS
  • SIMS
  • Laser Ablation
  • Boron Isotopes

A Review on the determination of Isotope Ratios of Boron with Mass Spectrometry

Suresh Kumar Aggarwal (1,2) and Chen-Feng You (2,3)

1) Fuel Chemistry Division, Bhabha Atomic Research Centre, Mumbai, India, 2)Department of Earth Sciences, National Cheng Kung University, Tainan, Taiwan, 3) Earth Dynamic System Research Centre, NCKU, Taiwan

Mass Spectrometry Reviews (2016), V9999, pp1–21, doi: 10.1002/mas.21490

Goal: The present review discusses different mass spectrometric techniques—viz, thermal ionization mass spectrometry (TIMS), inductively coupled plasma mass spectrometry (ICPMS), and secondary ion mass spectrometry SIMS)—used to determine 11B/10B isotope ratio, and concentration of boron required for various applications in earth sciences, marine geochemistry, nuclear technology, environmental, and agriculture sciences, etc.