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A combined chemical imaging approach using (MC) LA-ICP-MS and NIR-HSI to evaluate the diagenetic status of bone material for Sr isotope analysis

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Abstract

This paper presents a combination of elemental and isotopic spatial distribution imaging with near-infrared hyperspectral imaging (NIR-HSI) to evaluate the diagenetic status of skeletal remains. The aim is to assess how areas with biogenic n(87Sr)/n(86Sr) isotope-amount ratios may be identified in bone material, an important recorder complementary to teeth. Elemental (C, P, Ca, Sr) and isotopic (n(87Sr)/n(86Sr)) imaging were accomplished via laser ablation (LA) coupled in a split stream to a quadrupole inductively coupled plasma mass spectrometer (ICP-QMS) and a multicollector inductively coupled plasma mass spectrometer (MC ICP-MS) (abbreviation for the combined method LASS ICP-QMS/MC ICP-MS). Biogenic areas on the bone cross section, which remained unaltered by diagenetic processes, were localized using chemical indicators (I(C)/I(Ca) and I(C) × 10/I(P) intensity ratios) and NIR-HSI at a wavelength of 1410 nm to identify preserved collagen. The n(87Sr)/n(86Sr) isotope signature analyzed in these areas was in agreement with the biogenic bulk signal revealed by solubility profiling used as an independent method for validation. Elevated C intensities in the outer rim of the bone, caused by either precipitated secondary minerals or adsorbed humic materials, could be identified as indication for diagenetic alteration. These areas also show a different n(87Sr)/n(86Sr) isotopic composition. Therefore, the combination of NIR-HSI and LASS ICP-QMS/MC ICP-MS allows for the determination of preserved biogenic n(87Sr)/n(86Sr) isotope-amount ratios, if the original biogenic material has not been entirely replaced by diagenetic material.

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Abbreviations

ICP-QMS:

Inductively coupled plasma quadrupole mass spectrometer

LA:

Laser ablation

LASS ICP-QMS/MC ICP-MS:

Laser ablation coupled via a split stream to a quadrupole inductively coupled plasma mass spectrometer and a multicollector inductively coupled plasma mass spectrometer

MC ICP-MS:

Multicollector inductively coupled plasma mass spectrometer

NIR:

Near-infrared

NIR-HSI:

Near-infrared hyperspectral imaging

PCA:

Principal component analysis

ROI:

Region of interest

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Acknowledgments

The authors would like to acknowledge Maria Teschler-Nicola as former director of the Department of Anthropology at the Museum of Natural History, Vienna, who permitted the use and selected the human femur samples of this study in 2015. The authors would like to acknowledge Barbara Hinterstoisser from the University of Natural Resources and Life Sciences (Vienna, Austria) for enabling access to the NIR-HSI instrument. Very warm thanks to Ferenc Firtha from Szent Istvan University (Budapest, Hungary), who provided us with his expertise in NIR-HSI measurements/setup, who placed his software tools (Cubrowser, Argus) at our disposal and taught us how to use it. Furthermore, the authors would like to acknowledge the two anonymous reviewers for their positive and constructive feedback, which helped to improve this manuscript. Finally, we would like to thank Melanie Diesner and Tine Opper (VIRIS Laboratory) for their support in the lab.

Funding

This project was supported by the COMET-K1 competence center FFoQSI. The COMET-K1 competence center FFoQSI is funded by the Austrian ministries BMVIT, BMDW, and the Austrian provinces Niederoesterreich, Upper Austria, and Vienna within the scope of COMET - Competence Centers for Excellent Technologies. The program COMET is handled by the Austrian Research Promotion Agency FFG. We acknowledge the ERASMUS+ program for financial support.

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Authors and Affiliations

  1. Department of Chemistry, Division of Analytical Chemistry, VIRIS Laboratory, University of Natural Resources and Life Sciences, Vienna, Konrad-Lorenz-Str. 24, 3430, Tulln, Austria

    Anika Retzmann, Andreas Zitek, Johanna Irrgeher & Thomas Prohaska

  2. Archaeology Institute, University of the Highlands and Islands, Kirkwall, Orkney, KW15 1LX, UK

    Magdalena Blanz

  3. College of Physical Sciences, Department of Chemistry, Trace Element Speciation Laboratory Aberdeen (TESLA), University of Aberdeen, Meston Walk, Aberdeen, AB24 3UE, UK

    Magdalena Blanz & Jörg Feldmann

  4. FFoQSI - Austrian Competence Centre for Feed and Food Quality, Safety & Innovation, FFoQSI GmbH, Technopark 1C, 3430, Tulln, Austria

    Andreas Zitek

  5. Institute of Coastal Research, Marine Bioanalytical Chemistry, Helmholtz-Zentrum Geesthacht, Max-Planck Str. 1, 21502, Geesthacht, Germany

    Johanna Irrgeher

  6. Department of Anthropology, Museum of Natural History, Burgring 7, 1010, Vienna, Austria

    Maria Teschler-Nicola

  7. Department of Evolutionary Anthropology, University of Vienna, Althanstrasse 14, 1090, Vienna, Austria

    Maria Teschler-Nicola

  8. Chair of General and Analytical Chemistry, Montanuniversität Leoben, Franz Josef Str. 18, 8700, Leoben, Austria

    Thomas Prohaska

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  1. Anika Retzmann
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Published in the topical collection Elemental and Molecular Imaging by LA-ICP-MS with guest editor Beatriz Fernández García.

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Retzmann, A., Blanz, M., Zitek, A. et al. A combined chemical imaging approach using (MC) LA-ICP-MS and NIR-HSI to evaluate the diagenetic status of bone material for Sr isotope analysis. Anal Bioanal Chem 411, 565–580 (2019). https://doi.org/10.1007/s00216-018-1489-5

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