Hostname: page-component-78c5997874-ndw9j Total loading time: 0 Render date: 2024-11-19T08:18:56.971Z Has data issue: false hasContentIssue false

Compound-Specific Radiocarbon Dating of Essential and Non-Essential Amino Acids: Towards Determination of Dietary Reservoir Effects in Humans

Published online by Cambridge University Press:  09 February 2016

Shweta Nalawade-Chavan
Affiliation:
Research Laboratory for Archaeology and the History of Arts, University of Oxford, Oxford OX1 3QY, United Kingdom
James McCullagh
Affiliation:
Chemistry Research Laboratory, University of Oxford, Oxford OX1 3TA, United Kingdom
Robert Hedges
Affiliation:
Research Laboratory for Archaeology and the History of Arts, University of Oxford, Oxford OX1 3QY, United Kingdom
Clive Bonsall
Affiliation:
School of History, Classics and Archaeology, University of Edinburgh, Edinburgh EH8 9AG, United Kingdom
Adina Boroneanţ
Affiliation:
‘Vasile Pârvan’ Institute of Archaeology, Romanian Academy, 11 Henri Coandą St., 010667 Bucharest, Romania
Christopher Bronk Ramsey
Affiliation:
Research Laboratory for Archaeology and the History of Arts, University of Oxford, Oxford OX1 3QY, United Kingdom
Thomas Higham
Affiliation:
Research Laboratory for Archaeology and the History of Arts, University of Oxford, Oxford OX1 3QY, United Kingdom

Abstract

When humans consume foods from different radiocarbon reservoirs offset in age to the atmosphere, inaccuracies in the 14C date of bone collagen can occur. Mesolithic human skeletons from the Iron Gates section of the Lower Danube Valley have yielded reservoir offsets of up to ∼500 yr. This has been demonstrated through direct dating of bulk collagen from human bones and the remains of ungulate bone projectile points that were found embedded in them (Cook et al. 2001). We present improvements to a novel HPLC method for the detection and separation of underivatized amino acids using a water-only mobile phase free of organic or inorganic modifiers, ensuring very low carbon backgrounds. Our hypothesis is that direct 14C dating of single essential and non-essential amino acids might allow an improvement in the dating accuracy for reservoir-affected human bones. The method facilitates separation of less polar amino acids (mostly “essential”), currently not possible in the recently published protocol. We discuss methodological developments, demonstrate carbon backgrounds, and present analytical approaches to minimize their effects. We validate the precision and accuracy of the method by accelerator mass spectrometry (AMS) dating relatively modern and 14C-dead, known-age bone standards. Finally, we apply the method to the dating of single amino acids from bone samples with a proven ∼500–yr carbon reservoir effect from Mesolithic burials at the Iron Gates sites. We investigate whether differences can be found in AMS dates for essential and non-essential amino acids since, although contemporaneous, these are expected to derive from dietary sources with differing 14C reservoirs.

Type
Articles
Copyright
Copyright © 2013 by the Arizona Board of Regents on behalf of the University of Arizona 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Ambrose, S, Norr, L. 1993. Experimental evidence for the relationship of the carbon isotope ratios of whole diet and dietary protein to those of bone collagen and carbonate. In: Lambert, JB, Grupe, G, editors. Prehistoric Human Bone: Archaeology at the Molecular Level. Berlin: Springer. p 137.Google Scholar
Beavan, N, Sparks, R. 1998. Factors influencing 14C ages of the Pacific rat Rattus exulans. Radiocarbon 40(2): 601–13.Google Scholar
Beavan-Athfield, N, McFadgen, B, Sparks, J. 2001. Environmental influences on dietary carbon and 14C ages in modern rats and other species. Radiocarbon 43(1): 714.CrossRefGoogle Scholar
Brock, F, Higham, T, Ditchfield, P, Bronk Ramsey, C. 2010. Current pretreatment methods for AMS radiocarbon dating at the Oxford Radiocarbon Accelerator Unit (ORAU). Radiocarbon 52(1):103–12.CrossRefGoogle Scholar
Bronk Ramsey, C, Ditchfield, P, Humm, M. 2004a. Using a gas ion source for radiocarbon AMS and GC-AMS. Radiocarbon 46(1):2532.CrossRefGoogle Scholar
Bronk Ramsey, C, Higham, T, Leach, P. 2004b. Toward high-precision AMS: progress and limitations. Radiocarbon 46(1): 1724.CrossRefGoogle Scholar
Bruns, M, Levin, I, Munnich, K, Hubberten, H, Fillipakis, S. 1980. Regional sources of volcanic carbon dioxide and their influence on 14C content of present-day plant material. Radiocarbon 22(2):532–6.CrossRefGoogle Scholar
Cook, G, Bonsall, C, Hedges, REM, McSweeney, K, Boroneanţ, V, Pettitt, PB. 2001. A freshwater diet derived 14C reservoir effect at the Stone Age sites in the Iron Gates gorge. Radiocarbon 43(2A):453–60.CrossRefGoogle Scholar
Cook, GT, Bonsall, C, Hedges, REM, McSweeney, K, Boroneanţ, V, Bartosiewicz, L, Pettitt, PB. 2002. Problems of dating human bones from the Iron Gates. Antiquity 76(291):7785.CrossRefGoogle Scholar
Devlin, T. 1998. Textbook of Biochemistry with Clinical Correlations. 3rd edition. New York: Wiley-Liss.Google Scholar
Higham, T, Warren, R, Belinskij, A, Härke, H, Wood, R. 2010. Radiocarbon dating, stable isotope analysis, and diet-derived offsets in 14C ages from the Klin-Yar site, Russian North Caucasus. Radiocarbon 52(2):653–70.CrossRefGoogle Scholar
Jim, S, Jones, V, Ambrose, S, Evershed, R. 2006. Quantifying dietary macronutrient sources of carbon for bone collagen biosynthesis using natural abundance stable carbon isotope analysis. British Journal of Nutrition 95(6): 1005–62.CrossRefGoogle ScholarPubMed
Lambert, B, Grupe, G. 1993. Prehistoric Human Bone: Archaeology at the Molecular Level. Berlin: Springer.CrossRefGoogle Scholar
Longin, R. 1971. New method of collagen extraction for radiocarbon dating. Nature 230(5291):241–2.CrossRefGoogle ScholarPubMed
McCullagh, J, Marom, A, Hedges, R. 2010. Radiocarbon dating of individual amino acids from archaeological bone collagen. Radiocarbon 52(2):620–34.CrossRefGoogle Scholar
Marom, A, McCullagh, J, Higham, T, Sinitsyn, A, Hedges, R. 2012. Single amino acid radiocarbon dating of Upper Paleolithic modern humans. Proceedings of the National Academy of Sciences of the USA 109(17): 6878–81.CrossRefGoogle ScholarPubMed
O'Connell, T, Hedges, R. 1999. Isotopic comparison of hair and bone: archaeological analyses. Journal of Archaeological Science 26(6):661–5.Google Scholar
O'Connell, T, Healey, M, Hedges, R, Simpson, AHW. 2001. Isotopic comparison of hair, bone and nail: modern analyses. Journal of Archaeological Science 28(11): 1247–55.CrossRefGoogle Scholar
Reeds, P. 2000. Dispensable and indispensable amino acids for humans. Journal of Nutrition 130(7):1835S1840S.CrossRefGoogle ScholarPubMed
Reimer, PJ, Baillie, MGL, Bard, E, Bayliss, A, Beck, WJ, Bertrand, C, Blackwell, PG, Buck, CE, Burr, GS, Cutler, KB, Damon, PE, Edwards, RL, Fairbanks, RG, Friedrich, M, Guilderson, TP, Hughen, KA, Kromer, B, McCormac, FG, Manning, S, Bronk Ramsey, C, Reimer, RW, Remmele, S, Southon, JR, Stuiver, M, Talamo, S, Taylor, FW, van der Plicht, J, Weyhenmeyer, CE. 2004. IntCal04 terrestrial radiocarbon age calibration, 0–26 cal kyr BP. Radiocarbon 46(3): 1029–58.Google Scholar
Reimer, PJ, Baillie, MGL, Bard, E, Bayliss, A, Beck, JW, Blackwell, PG, Bronk Ramsey, C, Buck, CE, Burr, GS, Edwards, RL, Friedrich, M, Grootes, PM, Guilderson, TP, Hajdas, I, Heaton, T, Hogg, AG, Hughen, KA, Kaiser, KF, Kromer, B, McCormac, FG, Manning, SW, Reimer, RW, Richards, DA, Southon, JR, Talamo, S, Turney, CSM, van der Plicht, J, Weyhenmeyer, CE. 2009. IntCal09 and Marine09 radiocarbon age calibration curves, 0–50,000 years cal BP. Radiocarbon 51(4): 1111–50.CrossRefGoogle Scholar
Ward, G, Wilson, S. 1978. Procedures for comparing and combining radiocarbon age determinations: a critique. Archaeometry 20(1): 1931.CrossRefGoogle Scholar