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Direct application of compound-specific radiocarbon analysis of leaf waxes to establish lacustrine sediment chronology

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Abstract

This study demonstrates use of compound-specific radiocarbon analysis (CSRA) for dating Holocene lacustrine sediments from carbonate-hosted Ordy Pond, O‘ahu, Hawai‘i. Long-chain odd-numbered normal alkanes (n-alkanes), biomarkers characteristic of terrestrial higher plants, were ubiquitous in Ordy Pond sediments. The δ13C of individual n-alkanes ranged from −29.9 to −25.5‰, within the expected range for n-alkanes synthesized by land plants using the C3 or C4 carbon fixation pathway. The 14C ages of n-alkanes determined by CSRA showed remarkably good agreement with 14C dates of rare plant macrofossils obtained from nearby sedimentary horizons. In general, CSRA of n-alkanes successfully refined the age-control of the sediments. The sum of n-alkanes in each sample produced 70–170 μg of carbon (C), however, greater age errors were confirmed for samples containing less than 80 μg of C. The 14C age of n-alkanes from one particular sedimentary horizon was 4,155 years older than the value expected from the refined age-control, resulting in an apparent and arguable age discrepancy. Several lines of evidence suggest that this particular sample was contaminated by introduction of 14C-free C during preparative capillary gas chromatography. This study simultaneously highlighted the promising potential of CSRA for paleo-applications and the risks of contamination associated with micro-scale 14C measurement of individual organic compounds.

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References

  • Athens JS, Ward JV, Tuggle HD, Welch DJ, Blinn DW, Cowie R, Murakami GM, Sherman C (1999) Environment, vegetation change, and early human settlement on the ‘Ewa Plain: a cultural resource inventory of Naval Air Station, Barbers Point, O‘ahu, Hawai‘i, Part III: paleoenvironmental investigations. International Archeological Research Institute Inc., Honolulu, HI

    Google Scholar 

  • Athens JS, Tuggle HD, Ward JV, Welch DJ (2002) Avifaunal extinctions, vegetation change, and Polynesian impacts in prehistoric Hawai‘i. Archaeol Ocean 37:57–78

    Google Scholar 

  • Baker EA (1974) The influence of environment on leaf wax development in Brassica oleracea var. gemmifera. New Phytol 73:955–966

    Article  CAS  Google Scholar 

  • Bird MI, Summons RE, Gagan MK, Roksandic Z, Dowling L, Head J, Fifield LK, Cresswell RG, Johnson DP (1995) Terrestrial vegetation change inferred from n-alkane δ13C analysis in the marine environment. Geochim Cosmochim Acta 59:2853–2857

    Article  CAS  Google Scholar 

  • Björck S, Bennike O, Possnert G, Wohlfarth B, Digerfeldt G (1998) A high-resolution 14C dated sediment sequence from southwest Sweden: age comparisons between different components of the sediment. J Quat Sci 13:85–89

    Article  Google Scholar 

  • Bouloubassi I, Fillaux J, Saliot A (2001) Hydrocarbons in surface sediments from the Changjiang (Yangtze River) estuary, East China Sea. Mar Pollut Bull 42:1335–1346

    Article  CAS  Google Scholar 

  • Bourbonniere RA, Meyers PA (1996) Sedimentary geolipid records of historical changes in the watersheds and productivities of Lakes Ontario and Erie. Limnol Oceanogr 41:352–359

    Article  Google Scholar 

  • Bradley RS (1999) Paleoclimatology: reconstructing climates of the quaternary, 2nd edn. Academic Press, San Diego, CA

    Google Scholar 

  • Brincat D, Yamada K, Ishiwatari R, Uemura H, Naraoka H (2000) Molecular-isotopic stratigraphy of long-chain n-alkanes in Lake Baikal Holocene and glacial sediments. Org Geochem 31:287–294

    Article  CAS  Google Scholar 

  • Chikaraishi Y, Naraoka H (2003) Compound-specific δD-δ13C analyses of n-alkanes extracted from terrestrial and aquatic plants. Phytochemistry 63:361–371

    Article  CAS  Google Scholar 

  • Collister JW, Rieley G, Stern B, Eglinton G, Fry B (1994) Compound-specific δ13C analyses of leaf lipids from plants with differing carbon dioxide metabolisms. Org Geochem 21:619–627

    Article  CAS  Google Scholar 

  • Conte MH, Weber JC, Carlson PJ, Flanagan LB (2003) Molecular and carbon isotopic composition of leaf wax in vegetation and aerosols in a northern prairie ecosystem. Oecologia 135:67–77

    Google Scholar 

  • Cranwell PA (1981) Diagenesis of free and bound lipids in terrestrial detritus deposited in a lacustrine sediment. Org Geochem 14:1–14

    Google Scholar 

  • Dye T (1994) Apparent ages of marine shells: implications for archaeological dating in Hawai‘i. Radiocarbon 36:51–57

    CAS  Google Scholar 

  • Eglinton G, Hamilton RJ (1967) Leaf epicuticular waxes. Science 156:1322–1335

    Article  CAS  Google Scholar 

  • Eglinton TI, Aluwihare LI, Bauer JE, Druffel ERM, McNichol AP (1996) Gas chromatographic isolation of individual compounds from complex matrices for radiocarbon dating. Anal Chem 68:904–912

    Article  CAS  Google Scholar 

  • Eglinton TI, Benitez-Nelson BC, Pearson A, McNichol AP, Bauer JE, Druffel ERM (1997) Variability in radiocarbon ages of individual organic compounds from marine sediments. Science 277:796–799

    Article  CAS  Google Scholar 

  • Garrison GH (2002) Holocene sedimentary and aquatic biogeochemical responses reflected in Ordy Pond, Oah‘u, Hawai‘i and contemporary modeling of submarine groundwater discharge in Kahana Bay, Oah‘u, Hawai‘i. Ph.D. Dissertation, Department of Geology and Geophysics, University of Hawai‘i at Mānoa

  • Goodfriend GA, Hood DG (1983) Carbon isotope analysis of land snail shells: implications for carbon sources and radiocarbon dating. Radiocarbon 25:810–830

    Google Scholar 

  • Goodfriend GA, Stipp JJ (1983) Limestone and the problem of radiocarbon dating of land-snail shell carbonate. Geology 11:575–577

    Article  CAS  Google Scholar 

  • Goodfriend GA, Ellis GL, Toolin LJ (1999) Radiocarbon age anomalies in land snail shells from Texas: ontogenetic, individual, and geographic patterns of variation. Radiocarbon 41:149–156

    Google Scholar 

  • Hallam ND (1970) Growth and regeneration of waxes on the leaves of Eucalyptus. Planta 93:257–268

    Article  Google Scholar 

  • Hoefs MJL, Rijpstra WIC, Sinninghe Damsté JS (2002) The influence of oxic degradation on the sedimentary biomarker record I: evidence from Madeira Abyssal Plain turbidites. Geochim Cosmochim Acta 66:2719–2735

    Article  CAS  Google Scholar 

  • Hoering TC, Freeman DH (1984) Shape-selective sorption of monomethylalkanes by silicalite, a zeolite form of silica. J Chromatogr 316:333–341

    Article  CAS  Google Scholar 

  • Huang Y, Eglinton G, Ineson P, Latter PM, Bol R, Harkness DD (1997) Absence of carbon isotope fractionation of individual n-alkanes in a 23-year field decomposition experiment with Calluna vulgaris. Org Geochem 26:497–501

    Article  CAS  Google Scholar 

  • Ishiwatari R, Uzaki M, Yamada K (1994) Carbon isotope compositions of individual n-alkanes in recent sediments. Org Geochem 21:801–808

    Article  CAS  Google Scholar 

  • Kenig F, Popp BN, Summons RE (2000) Preparative HPLC with ultrastable-Y zeolite for compound-specific carbon isotopic analyses. Org Geochem 31:1087–1094

    Article  CAS  Google Scholar 

  • Ku T-L, Kimmel MA, Easton WH, O’Neil TJ (1974) Eustatic sea level 120,000 years ago on O‘ahu, Hawai‘i. Science 183:95a

    Article  Google Scholar 

  • Kunst A, Samuels AL (2003) Biosynthesis and secretion of plant cuticular wax. Prog Lipid Res 42:51–80

    Article  CAS  Google Scholar 

  • Kuypers MMM, Pancost RD, Sinninghe Damsté JS (1999) A large and abrupt fall in atmospheric CO2 concentrations during Cretaceous times. Nature 399:342–345

    Article  CAS  Google Scholar 

  • Lowe JJ, Walker MJC (2000) Radiocarbon dating the last glacial-interglacial transition (Ca. 14-9 14C ka BP) in terrestrial and marine records: the need for new quality assurance protocols. Radiocarbon 42:53–68

    CAS  Google Scholar 

  • Mazeas L, Budzinski H, Raymond N (2002) Absence of stable carbon isotope fractionation of saturated and polycyclic aromatic hydrocarbons during aerobic bacterial biodegradation. Org Geochem 33:1259–1272

    Article  CAS  Google Scholar 

  • McNichol AP, Gagnon AR, Osborne EA, Hutton DL, von Reden KF, Schneider RJ (1995) Improvements in procedural blanks at NOSAMS: reflection of improvements in sample preparation and accelerator operation. Radiocarbon 37:683–691

    CAS  Google Scholar 

  • McNichol AP, Jull AJT, Burr GS (2001) Converting AMS data to radiocarbon values: considerations and conventions. Radiocarbon 43:313–320

    Google Scholar 

  • Menzel D, Schouten S, van Bergen PF, Sinninghe Damsté JS (2004) Higher plant vegetation changes during Pliocene sapropel formation. Org Geochem 35:1343–1353

    CAS  Google Scholar 

  • Mollenhauer G, Kienast M, Lamy F, Meggers H, Schneider RR, Hayes JM, Eglinton TI (2005) An evaluation of 14C age relationships between co-occuring foraminifera, alkenones, and total organic carbon in continental margin sediments. Paleoceanography, 20, PA1016, doi:10.1029/2004PA001103

  • Muri G, Wakeham SG, Pease TK, Faganeli J (2004) Evaluation of lipid biomarkers as indicators of changes in organic matter delivery to sediments from Lake Planina, a remote mountain lake in NW Slovenia. Org Geochem 35:1083–1093

    Article  CAS  Google Scholar 

  • Ogden (1999) Remedial investigation report for BRAC—related activities, regional ground-water system, Naval Air Station Barbers Point, O‘ahu, Hawai‘i vol 3. Ogden Environmental and Energy Services Company Inc, Honolulu, Hawai‘i

    Google Scholar 

  • Ohkouchi N, Eglinton TI, Hayes JM (2003) Radiocarbon dating of individual fatty acids as a tool for refining Antarctic margin sediment chronologies. Radiocarbon 45:17–24

    CAS  Google Scholar 

  • Pearson A (1999) Biogeochemical applications of compound-specific radiocarbon analysis. Ph.D. Dissertation, Joint program in oceanography/applied ocean science and engineering. Massachusetts Institute of Technology/Woods Hole Oceanographic Institution

  • Pearson A, Eglinton TI (2000) The origin of n-alkanes in Santa Monica Basin surface sediment: a model based on compound-specific Δ14C and δ13C data. Org Geochem 31:1103–1116

    Article  CAS  Google Scholar 

  • Pearson A, McNichol AP, Schneider RJ, von Reden KF, Zheng Y (1998) Microscale AMS 14C measurement at NOSAMS. Radiocarbon 40:61–75

    Google Scholar 

  • Pearson A, Eglinton TI, McNichol AP (2000) An organic tracer for surface ocean radiocarbon. Paleoceanography 15:541–550

    Article  Google Scholar 

  • Pearson A, McNichol AP, Benitez-Nelson BC, Hayes JM, Eglinton TI (2001) Origins of lipid biomarkers in Santa Monica Basin surface sediment: a case study using compound-specific Δ14C analysis. Geochim Cosmochim Acta 65:3123–3137

    Article  CAS  Google Scholar 

  • Petsch ST, Eglinton TI, Edwards KJ (2001) 14C-dead living biomass: evidence for microbial assimilation of ancient organic carbon during shale weathering. Science 292:1127–1131

    Article  CAS  Google Scholar 

  • Reddy CM, Pearson A, Xu L, McNichol AP, Benner Jr BA, Wise SA, Klouda GA, Currie LA, Eglinton TI (2002) Radiocarbon as a tool to apportion the sources of polycyclic aromatic hydrocarbons and black carbon in environmental samples. Environ Sci Technol 36:1774–1782

    Article  CAS  Google Scholar 

  • Reddy CM, Xu L, O’Connor R (2003) Using radiocarbon to apportion sources of polycyclic aromatic hydrocarbons in household soot. Environ Forensic 4:191–197

    Article  CAS  Google Scholar 

  • Reimer PJ, Baillie MGL, Bard E, Bayliss A, Beck JW, Bertrand CJH, Blackwell PG, Buck CE, Burr GS, Cutler KB, Damon PE, Edwards RL, Fairbanks RG, Friedrich M, Guilderson TP, Hogg AG, Hughen KA, Kromer B, McCormac FG, Manning SW, Ramsey CB, Reimer RW, Remmele S, Southon JR, Stuiver M, Talamo S, Taylor FW, van der Plicht J, Weyhenmeyer CE (2004) IntCal04 terrestrial radiocarbon age calibration, 26–0 ka BP. Radiocarbon 46:1029–1058

    CAS  Google Scholar 

  • Rieley G, Collier RJ, Jones DM, Eglinton G, Eakin PA, Fallick AE (1991) Sources of sedimentary lipids deduced from stable carbon-isotope analyses of individual compounds. Nature 352:425–427

    Article  CAS  Google Scholar 

  • Schefuß E, Ratmeyer V, Stutt J-BW, Jansen JHF, Sinninghe Damsté JS (2003) Carbon isotope analyses of n-alkanes in dust from the lower atmosphere over the central eastern Atlantic. Geochim Cosmochim Acta 67:1757–1767

    Article  CAS  Google Scholar 

  • Sherman CE, Glenn CR, Jones AT, Burnett WC, Schwarcz HP (1993) New evidence for two highstands of the sea during the last interglacial, oxygen isotope substage 5e. Geology 21:1079–1082

    Article  Google Scholar 

  • Smittenberg RH, Hopmans EC, Schouten S, Hayes JM, Eglinton TI, Sinninghe Damsté JS (2004) Compound-specific radiocarbon dating of the varved Holocene sedimentary record of Saanich Inlet, Canada. Paleoceanography, 19, PA2012, doi:10.1029/2003PA000927

  • Smittenberg RH, Eglinton TI, Schouten S, Sinninghe Damsté JS (2006) Ongoing buildup of refractory organic carbon in boreal soils during the Holocene. Science 314:1283–1286

    Article  CAS  Google Scholar 

  • Stuiver M, Polach HA (1977) Discussion: reporting of 14C data. Radiocarbon 19:355–363

    Google Scholar 

  • Stuiver M, Reimer PJ (1993) Extended 14C database and revised CALIB radiocarbon calibration program. Radiocarbon 35:215–230

    Google Scholar 

  • Stuiver M, Reimer PJ, Reimer RW (2005) CALIB 5.0. [WWW program and documentation: http://calib.qub.ac.uk/calib]

  • Sun MY, Wakeham SG (1994) Molecular evidence for degradation and preservation of organic matter in the anoxic Black Sea Basin. Geochim Cosmochim Acta 58:3395–3406

    Article  CAS  Google Scholar 

  • Sun Y, Chen Z, Xu S, Cai P (2005) Stable carbon and hydrogen isotopic fractionation of individual n-alkanes accompanying biodegradation: evidence from a group of progressively biodegraded oils. Org Geochem 36:225–238

    Article  CAS  Google Scholar 

  • Szabo BJ, Ludwig KR, Muhs DR, Simmons KR (1994) Thorium−230 ages of corals and duration of the last interglacial sea-level high stand on O‘ahu, Hawai‘i. Science 266:93–96

    Article  CAS  Google Scholar 

  • Törnqvist TE, de Jong AFM, Oosterbaan WA, van der Borg K (1992) Accurate dating of organic deposit by AMS 14C measurement of macrofossils. Radiocarbon 34:566–577

    Google Scholar 

  • Tribble JS, Athens JS, Allen CB, Frankel E, Skilbeck CG (1998) A high resolution sedimentary record of O‘ahu Holocene history. GSA Abstracts with programs, 1998 Annual Meeting, Toronto, Canada, A-162

  • Tribble JS, Garrison GH, Athens JS, Allen CB, Skilbeck CG, Frankel E (1999) Evidence for Early-Mid Holocene sea-level on O‘ahu, Hawai‘i from coastal pond sediments. In: Fletcher CH, Matthews JV (eds) The non-steady state of the inner sheld and shoreline: coastal change on the time scale of decades to millennia in the late quaternary. Inaugural meeting of IGCP Project #437 “Coastal Environmental Change During Sea Level Highstands,” Abstracts with Program. University of Hawai‘i, Honolulu, USA, November 1999, pp 215–218

  • Turney CSM, Coope GR, Harkness DD, Lowe JJ, Walker MJC (2000) Implications for the dating of Wisconsinan (Weichselian) late-glacial events of systematic radiocarbon age differences between terrestrial plant macrofossils from a site in SW Ireland. Quat Res 53:114–121

    Article  CAS  Google Scholar 

  • Uchida M, Shibata Y, Ohkushi K, Yoneda M, Kawamura K, Morita M (2005) Age discrepancy between molecular biomarkers and calcareous foraminifera isolated from the same horizons of Northwest Pacific sediments. Chem Geol 218:73–89

    Article  CAS  Google Scholar 

  • Vance RE, Telka AM (1998) Accelerator mass spectrometry radiocarbon dating of 1994 Lake Winnipeg cores. J Paleolimnol 19:329–334

    Article  Google Scholar 

  • von Reden KF, McNichol AP, Pearson A, Schneider RJ (1998) 14C AMS measurements of <100 μg samples with a high-current system. Radiocarbon 40:247–253

    Google Scholar 

  • Walker MJC, Bryant C, Coope GR, Harkness DD, Lowe JJ, Scott EM (2001) Towards a radiocarbon chronology of the late-glacial: sample selection strategies. Radiocarbon 43:1007–1019

    CAS  Google Scholar 

  • Wirthensohn MG, Sedgley M (1996) Epicuticular wax structure and regeneration on developing juvenile Eucalyptus leaves. Aust J Bot 44:691–704

    Article  Google Scholar 

  • Wu Y, Zhang J, Mi T, Li B (2001) Occurrence of n-alkanes and polycyclic aromatic hydrocarbons in the core sediments of the Yellow Sea. Mar Chem 76:1–15

    Article  CAS  Google Scholar 

  • Yamada K, Ishiwatari R (1999) Carbon isotopic compositions of long-chain n-alkanes in the Japan Sea sediments: implications for paleoenvironmental changes over the past 85 kyr. Org Geochem 30:367–377

    Article  CAS  Google Scholar 

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Acknowledgements

The authors appreciate Dr. J. M. Hayes for his critical advice on the method development and data interpretations as well as the staff at the NOSAMS facility for analyzing the samples. We truly appreciate the kind assistance and technical support from R. J. Wallsgrove, T. Rust, and J. K. Tanimoto in the laboratory. We are grateful to Dr. C. I. Measures, M. Brown, and K. Kime, who hospitably allowed us to use their laboratory for sample preparations. We acknowledge significant contribution from Dr. S. J. Athens from International Archaeological Research Institute Inc. We would like to thank Dr. Eric J. Hochberg for his assistance on computer graphics. And lastly, constructive comments from the reviewers and editors tremendously improved the overall quality of our manuscript. This project was funded by Petroleum Research Fund (PRF # 40088-ACS) and in part by Sigma Xi, The Scientific Research Society (Grants in aid of research, 2003). This is SOEST contribution number 7092.

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Uchikawa, J., Popp, B.N., Schoonmaker, J.E. et al. Direct application of compound-specific radiocarbon analysis of leaf waxes to establish lacustrine sediment chronology. J Paleolimnol 39, 43–60 (2008). https://doi.org/10.1007/s10933-007-9094-1

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