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
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.
KeywordsDiagenesis LASS ICP-QMS/MC ICP-MS Near-infrared hyperspectral imaging Human bone remains
Inductively coupled plasma quadrupole mass spectrometer
- 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
Near-infrared hyperspectral imaging
Principal component analysis
Region of interest
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.
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.
Compliance with ethical standards
Conflict of interest
The authors declare that they have no conflict of interest.
- 1.Bentley RA. Strontium isotopes from the earth to the archaeological skeleton: a review. J Archaeol Method Theory. 2006;13(3):135–87.Google Scholar
- 6.Prohaska T, Teschler-Nicola M, Galler G, Přichystal A, Stingeder G, Jelenc M, et al. Non-destructive determination of 87Sr/86Sr isotope ratios in early upper Paleolithic human teeth from the Mladeč caves—preliminary results. In: Teschler-Nicola M, editor. Early modern humans at the Moravian Gate. Vienna: Springer-Verlag; 2006. p. 505–14. https://doi.org/10.1007/978-3-211-49294-9_18.Google Scholar
- 7.Horstwood MSA, Evans JA, Montgomery J. Determination of Sr isotopes in calcium phosphates using laser ablation inductively coupled plasma mass spectrometry and their application to archaeological tooth enamel. Geochim Cosmochim Acta. 2008;72(23):5659–74. https://doi.org/10.1016/j.gca.2008.08.016.Google Scholar
- 9.Copeland SR, Sponheimer M, Lee-Thorp JA, le Roux PJ, de Ruiter DJ, Richards MP. Strontium isotope ratios in fossil teeth from South Africa: assessing laser ablation MC-ICP-MS analysis and the extent of diagenesis. J Archaeol Sci. 2010;37(7):1437–46. https://doi.org/10.1016/j.jas.2010.01.003.Google Scholar
- 13.Capo RC, Stewart BW, Chadwick OA. Strontium isotopes as tracers of ecosystem processes: theory and methods. Geoderma. 1998;82:197–225.Google Scholar
- 15.Blum JD, Taliaferro EH, Weisse MT, HR T. Changes in Sr/Ca, Ba/Ca and 87Sr/86Sr ratios between two forest ecosystems in the northeastern USA. Biogeochemistry. 2000;49:87–101.Google Scholar
- 17.Grupe G, Price TD, Schröter P, Söllner F, Johnson CM, Beard BL. Mobility of Bell Beaker people revealed by strontium isotope ratios of tooth and bone: a study of southern Bavarian skeletal remains. Appl Geochem. 1997;12:517–25.Google Scholar
- 21.Ortega LA, Guede I, Zuluaga MC, Alonso-Olazabal A, Murelaga X, Niso J, et al. Strontium isotopes of human remains from the San Martín de Dulantzi graveyard (Alegría-Dulantzi, Álava) and population mobility in the Early Middle Ages. Quat Int. 2013;303:54–63. https://doi.org/10.1016/j.quaint.2013.02.008.Google Scholar
- 23.Wilson L, Pollard M. Here today, gone tomorrow? Integrated experimentation and geochemical modeling in studies of archaeological diagenetic change. Acc Chem Res. 2002;35(8):644–51.Google Scholar
- 24.Nelson B, Deniro MJ, Schoeninger MJ, De Paolo DJ. Effects of diagenesis on strontium, carbon, nitrogen and oxygen concentration and isotopic composition of bone. Geochim Cosmochim Acta. 1986;50:1941.Google Scholar
- 25.Kohn MJ, Schoeninger MJ, Barker WW. Altered states: effects of diagenesis on fossil tooth chemistry. Geochim Cosmochim Acta. 1999;63(18):2737–47.Google Scholar
- 29.Driessens FCM, Verbeeck RK. Biominerals. Boca Raton: CRC Press; 1990.Google Scholar
- 31.Price TD, Blitz J, Burton J, Ezzo JA. Diagenesis in prehistoric bone: problems and solutions. J Archaeol Sci. 1992;19(5):513–29.Google Scholar
- 32.Sillen A. Biogenic and diagenetic Sr/Ca in Plio-Pleistocene fossils of the Omo Shungura Formation. Paleobiology. 1986;12(3):311–23.Google Scholar
- 34.Trueman CN, Palmer MR, Field J, Privat K, Ludgate N, Chavagnac V, et al. Comparing rates of recrystallisation and the potential for preservation of biomolecules from the distribution of trace elements in fossil bones. Comptes Rendus Palevol. 2008;7(2):145–58. https://doi.org/10.1016/j.crpv.2008.02.006.Google Scholar
- 38.Willmes M, Kinsley L, Moncel MH, Armstrong RA, Aubert M, Eggins S, et al. Improvement of laser ablation in situ micro-analysis to identify diagenetic alteration and measure strontium isotope ratios in fossil human teeth. J Archaeol Sci. 2016;70:102–16. https://doi.org/10.1016/j.jas.2016.04.017.Google Scholar
- 39.Shemesh A. Crystallinity and diagenesis of sedimentary apatites. Geochim Cosmochim Acta. 1990;54(9):2433–8.Google Scholar
- 41.Greene EF, Tauch S, Webb E, Amarasiriwardena D. Application of diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) for the identification of potential diagenesis and crystallinity changes in teeth. Microchem J. 2004;76(1):141–9. https://doi.org/10.1016/j.microc.2003.11.006.Google Scholar
- 46.Longato S, Woss C, Hatzer-Grubwieser P, Bauer C, Parson W, Unterberger SH, et al. Post-mortem interval estimation of human skeletal remains by micro-computed tomography, mid-infrared microscopic imaging and energy dispersive X-ray mapping. Anal Methods. 2015;7(7):2917–27. https://doi.org/10.1039/c4ay02943g.Google Scholar
- 47.Woess C, Unterberger SH, Roider C, Ritsch-Marte M, Pemberger N, Cemper-Kiesslich J, et al. Assessing various infrared (IR) microscopic imaging techniques for post-mortem interval evaluation of human skeletal remains. PLoS One. 2017;12(3):e0174552. https://doi.org/10.1371/journal.pone.0174552.Google Scholar
- 49.Thomas D, McGoverin C, Chinsamy A, Manley M. Near infrared analysis of fossil bone from the Western Cape of South Africa. J Near Infrared Spectrosc. 2011;19(3):151–9.Google Scholar
- 52.Koehler FW, Lee IE, Kidder LH, Lewis EN. Near infrared spectroscopy: the practical chemical imaging solution. Spectrosc Eur. 2002;14(3).Google Scholar
- 54.ElMasry G, Sun D-W. CHAPTER 1 - principles of hyperspectral imaging technology. In: Sun D-W, editor. Hyperspectral imaging for food quality analysis and control. San Diego: Academic; 2010. p. 3–43. https://doi.org/10.1016/B978-0-12-374753-2.10001-2.Google Scholar
- 55.Firtha F. Argus hyperspectral acquisition software. 2010.Google Scholar
- 58.Galler P, Limbeck A, Boulyga SF, Stingeder G, Hirata T, Prohaska T. Development of an on-line flow injection Sr/ matrix separation method for accurate, high-throughput determination of Sr isotope ratios by multiple collector-inductively coupled plasma-mass spectrometry. Anal Chem. 2007;79:5023–9.Google Scholar
- 62.Irrgeher J, Galler P, Prohask T. 87Sr/86Sr isotope ratio measurements by laser ablation multicollector inductively coupled plasma mass spectrometry: reconsidering matrix interferences in bioapatites and biogenic carbonates. Spectrochim Acta B. 2016;125:31–42. https://doi.org/10.1016/j.sab.2016.09.008.Google Scholar
- 63.Draxler J, Zitek A, Meischel M, Stranzl-Tschegg SE, Mingler B, Martinelli E, et al. Regionalized quantitative LA-ICP-MS imaging of the biodegradation of magnesium alloys in bone tissue. J Anal At Spectrom. 2015. https://doi.org/10.1039/C5JA00354G10.1039/c5ja00354g.
- 64.Zitek A, Aleon J, Prohaska T. CHAPTER 9 chemical imaging. In: Prohaska T, Irrgeher J, Zitek A, Jakubowski N, editors. Sector field mass spectrometry for elemental and isotopic analysis: The Royal Society of Chemistry; 2015. p. 152–82. https://doi.org/10.1039/9781849735407-00152.
- 65.Schultheiss G. Analysis of isotope ratios in anthropological and archaeological samples by high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS). Vienna: University of Natural Resources and Life Sciences; 2003.Google Scholar
- 66.Theiner S. The use of strontium isotope ratio measurements by MC-ICP-MS for fundamental studies on diagenesis and for the reconstruction of animal migration at the Celtic excavation site Roseldorf Diplomarbeit. Vienna: University of Vienna; 2011.Google Scholar
- 68.Irrgeher J, Teschler-Nicola M, Leutgeb K, Weiß C, Kern D, Prohaska T. Migration and mobility in the latest Neolithic of the Traisen Valley, Lower Austria: Sr isotope analysis. In: Kaiser E, Burger J, Schier W, editors. Population dynamics in prehistory and early history. New approaches by using stable isotopes and genetics, vol. 5. Berlin, Boston: De Gruyter; 2012. p. 213–26. https://doi.org/10.1515/9783110266306.Google Scholar
- 73.Osborne BG. Near-infrared spectroscopy in food analysis. In: Encyclopedia of analytical chemistry. Major reference works: Wiley; 2006. p. 1–14. https://doi.org/10.1002/9780470027318.a1018.
- 75.White EM, Hannus LA. Chemical weathering of bone in archaeological soils. Am Antiq. 1983;48(2):316–22.Google Scholar