Abstract
A sediment core from Lake Koucha (eastern Tibetan Plateau) was investigated using organic biomarkers and their stable carbon isotope signatures. The correlation between TOC content, total amount of aquatic macrophyte-derived n-alkanes (e.g. nC23) and δ13C values of TOC and nC23 indicates that Lake Koucha was macrophyte-dominated before 8 cal ka BP. Shortly after the lake turned from a saline to a freshwater system at 7.2 cal ka BP, a variety of algal and bacterial markers such as hopanoids and isoprenoids emerged, of which phytane, pentamethylicosene (PMI), moretene and diploptene are particularly abundant. Phytane and PMI show different isotopic signals (≈−18 and ≈−28‰, respectively), which indicates that they originated from different sources. Phytane may have been derived from cyanobacteria, while methanogenic archaea may be the source of PMI. The isotopic depletion of diploptene and moretene (≈−60‰) indicates the presence of methanotrophs. After 6.1 cal ka BP, the saturated C20 highly branched isoprenoid (HBI) became the dominant constituent of the aliphatic hydrocarbon fraction. Such dominance has rarely been reported in lacustrine environments, and indicates a strong presence of algae (most likely diatoms) or cyanobacteria. At 4.7 cal ka BP, the appearance of an unsaturated C25 HBI, which is a specific biomarker for diatoms, was noted. Furthermore, the level of nC17-alkane was observed to increase in abundance in the uppermost two samples. These results suggest that the lake was phytoplankton-dominated during the last 6.1 ka. Relatively low biomarker concentrations and δ13C values at 6.0, 3.1 and 1.8 cal ka BP indicate the occurrence of cool periods, which is in agreement with inferences from other locations on the Tibetan Plateau. The δ13C values of nC23 range from −23.5 to −12.6‰, with high values at the peak of macrophyte abundance at ca. 11 cal ka BP and at the phytoplankton maximum between ca 6.1 and 2.8 cal ka BP. Thus, aquatic macrophyte-derived mid-chain n-alkanes have been found to be excellent indicators of carbon-limiting conditions, which lead to the assimilation of isotopically-enriched carbon species. The limitation of carbon sources could be a localized phenomenon occurring in dense plant stands (as in the older section of the core), or it may be induced by high primary productivity (as in the younger section). Since the δ13C value of the inorganic carbon source may vary, the offset between the δ13C values of nC23 and TIC could serve as a more precise proxy for carbon-limiting conditions in lacustrine environments, which could in turn be interpreted with respect to lacustrine paleo-productivity.
Similar content being viewed by others
References
Ageta H, Arai Y (1983) Fern constituents: pentacyclic triterpenoids isolated from Polypodium niponicum and P. formosamum. Phytochemistry 22:1801–1808
Allen ED, Spence DHN (1981) The differential ability of aquatic plants to utilize the inorganic carbon supply in fresh water. New Phytol 87:269–283
An CB, Feng ZD, Barton L (2006) Dry or humid? Mid-Holocene humidity changes in arid and semi-arid China. Quat Sci Rev 25:351–361
Belt ST, Massé G, Allard WG, Robert JM, Rowland SJ (2001a) Identification of a C25 highly branched isoprenoid triene in the freshwater diatom Navicula sclesvicensis. Org Geochem 32:1169
Belt ST, Massé G, Allard WG, Robert JM, Rowland SJ (2001b) C25 highly branched isoprenoid alkenes in planktonic diatoms of the Pleurosigma genus. Org Geochem 32:1271–1275
Blumenberg M, Seifert R, Kasten S, Bahlmann E, Michaelis W (2009) Euphotic zone bacterioplankton sources major sedimentary bacteriohopanepolyols in the Holocene Black Sea. Geochim Cosmochim Acta 73:750–766
Bond G, Showers W, Cheseby M, Lotti R, Almasi P, de Menocal P, Priore P, Cullen H, Haydas I, Bonani G (1997) A pervasive millennial-scale cycle in North Atlantic Holocene and Glacial climates. Science 278:1257–1266
Brassell SC, Wardroper AMK, Thomson ID, Maxwell JR, Eglinton G (1981) Specific acyclic isoprenoids as biological markers of methanogenic bacteria in marine sediments. Nature 290:693–696
Brush GS, Hilgartner WB (2000) Paleoecology of submerged macrophytes in the upper Chesapeake Bay. Ecol Monogr 70:645–667
Burkhardt S, Riebesell U, Zondervan I (1999) Effects of growth rate, CO2 concentration and cell size on the stable carbon isotope fractionation in marine phytoplankton. Geochim Cosmochim Acta 63:3729–3741
Chen F, Yu Z, Yang M, Ito E, Wang S, Madsen DB, Huang X, Zhao Y, Sato T, Birks HJB, Boomer I, Chen J, An C, Wünnemann B (2008) Holocene moisture evolution in arid central Asia and its out-of-phase relationship with Asian monsoon history. Quat Sci Rev 27:351–364
Deuser WG (1970) Isotopic evidence for diminishing supply for available carbon during diatom bloom in the Black Sea. Nature 225:1069–1071
Didyk BM, Simoneit BRT, Brassell SC, Eglinton G (1978) Organic geochemical indicators of palaeoenvironmental conditions of sedimentation. Nature 272:216–222
Dunlop RW, Jefferies PR (1985) Hydrocarbons of the hypersaline basins of Shark Bay, Western Australia. Org Geochem 8:313–320
Eglinton G, Hamilton RJ (1967) Leaf epicuticular waxes. Science 156:1322–1335
Elvert M, Suess E, Whiticar MJ (1999) Anaerobic methane oxidation associated with marine gas hydrates: superlight C-isotopes from saturated and unsaturated C20 and C25 irregular isoprenoids. Naturwissenschaften 86:295–300
Elvert M, Whiticar MJ, Suess E (2001) Diploptene in varved sediments of Saanich Inlet: indicator of increasing bacterial activity under anaerobic conditions during the Holocene. Mar Geol 174:371–383
Fan P, Wang D, Qi R (2004) Analysis on climatic feature and its change in source region of the Yellow River. J Qinghai Univ 22:19–24
Ficken KJ, Li B, Swain DL, Eglinton G (2000) An n-alkane proxy for the sedimentary input of submerged/floating freshwater aquatic macrophytes. Org Geochem 31:745–749
Fogel ML, Cifuentes LA (1993) Isotope fractionation during primary production. In: Engel MH, Macko SA (eds) Organic geochemistry: principles and applications. Plenum press, New York, pp 73–98
Freeman KH, Hayes JM, Trendel JM, Albrecht P (1990) Evidence from GC-MS carbon isotopic measurements for multiple origins of sedimentary hydrocarbons. Nature 353:627–644
Freeman KH, Wakeham SG, Hayes JM (1994) Predictive isotopic biogeochemistry: hydrocarbons from anoxic marine basins. Org Geochem 21:629–644
Gasse F, Fontes JC, VanCampo E, Wei K (1996) Holocene environmental changes in Bangong Co basin (western Tibet). 4. Discussion and conclusions. Palaeogeogr Palaeoclimatol Palaeoecol 120:79–92
Gelpi E, Schneider H, Mann J, Oró J (1970) Hydrocarbons of geochemical significance in microscopic algae. Phytochemistry 9:603–612
Gomes A, Azevedo D (2003) Aliphatic and aromatic hydrocarbons in tropical recent sediments of Campos dos Goytacazes, RJ, Brazil. J Braz Chem Soc 14:358–368
Grimalt JO, Yruela I, Saiz-Jimenez C, Toja J, DeLeeuw JW, Albaiges J (1991) Sedimentary lipid biogeochemistry of an hypereutrophic alkaline lagoon. Geochim Cosmochim Acta 55:2555–2577
Grossi V, Hirschler A, Raphel D, Rontani JF, De Leeuw JW, Bertrand JC (1998) Biotransformation pathways of phytol in recent anoxic sediments. Org Geochem 29:845–861
Gupta A, Anderson DM, Overpeck JT (2003) Abrupt changes in the Asian southwest monsoon during the Holocene and their links to the North Atlantic Ocean. Nature 421:354–357
Hanisch S, Ariztegui D, Puttmann W (2003) The biomarker record of Lake Albano, central Italy—implications for Holocene aquatic system response to environmental change. Org Geochem 34:1223–1235
Hayes JM, Freemann KH, Popp BN, Hoham CH (1990) Compound-specific isotopic analyses: a novel tool for reconstruction of ancient biogeochemical processes. Org Geochem 16:1115–1128
Herzschuh U (2006) Palaeo-moisture evolution at the margins of the Asian monsoon during the last 50 ka. Quat Sci Rev 25:163–178
Herzschuh U, Zhang C, Mischke S, Herzschuh R, Mohammadi F, Mingram B, Kürschner H, Riedel F (2005) A late Quaternary lake record from the Qilian Mountains (NW China): evolution of the primary production and the water depth reconstructed from macrofossil, pollen, biomarker, and isotope data. Glob Planet Change 46:361–379
Herzschuh U, Winter K, Wünnemann B, Li S (2006) A general cooling trend on the central Tibetan Plateau throughout the Holocene recorded by Lake Zigetang pollen spectra. Quat Int 154–155:113–121
Herzschuh U, Kramer A, Mischke S, Zhang C (2009) Quantitative climate and vegetation trends since the late glacial on the northeastern Tibetan Plateau deduced from Koucha Lake pollen spectra. Quat Res 71:162–171
Holzer G, Oro J, Tornabene TG (1979) Gas chromatography-mass spectrometric analysis of neutral lipids from methanogenic and thermoacidophilic bacteria. J Chromatogr 186:795–809
Huang YS, Street-Perrott FA, Perrot RA, Metzger P, Eglinton G (1999) Glacial-interglacial environmental changes inferred from molecular and compound-specific delta C-13 analyses of sediments from Sacred Lake, Mt. Kenya. Geochim Cosmochim Acta 63:1383–1404
Jaffe R, Mead R, Hernandez ME, Peralba MC, DiGuida OA (2001) Origin and transport of sedimentary organic matter in two subtropical estuaries: a comparative, biomarker-based study. Org Geochem 32:507–526
Kenig F, Sinninghe Damsté JS, Kock-van Dalen AC, Rijpstra WIC, Huc AY, de Leeuw JW (1995) Occurrence and origin of mono-, di-, and trimethylalkanes in modern and Holocene cyanobacterial mats from Abu Dhabi, United Arab Emirates. Geochim Cosmochim Acta 59:2999–3015
Kolattukudy PE, Croteau R, Buckner JS (1976) Biochemistry of plant waxes. In: Kolattukudy) PE (ed) Chemistry, biochemistry of natural waxes. Elsevier, Amsterdam, pp 289–347
Koopmans MP, Rijpstra WIC, Klapwijk MM, de Leeuw JW, Lewan MD, Sinninghe Damste’ JS (1999) A thermal and chemical degradation approach to decipher pristane and phytane precursors in sedimentary organic matter. Org Geochem 30:1089–1104
Kovats E (1958) Gas-chromatographic characterisation of organic compounds. Part 1. Retention indexes of aliphatic halides, alcohols, aldehydes and ketones. Helv Chim Acta 41:1915–1932
Kristen I, Wilkes H, Vieth A, Zink KG, Plessen B, Thorpe J, Oberhänsli H (2009) Biomarker and stable carbon isotope analyses of sedimentary organic matter from Lake Tswaing: evidence for deglacial wetness and early Holocene drought from South Africa. submitted to J. Paleolimn
Leng MJ, Marshall JD (2004) Palaeoclimate interpretation of stable isotope data from lake sediment archives. Quat Sci Rev 23:811–831
Li JG, Philip RP, Pu F, Allen J (1996) Long-chain alkenones in Qinghai lake sediments. Geochim Cosmochim Acta 60:235–241
Lichtfouse E, Derenne S, Mariotti A, Largeau C (1994) Possible algal origin of long chain odd n-alkanes in immature sediments as revealed by distributions and carbon isotope ratios. Org Geochem 22:1023–1027
Liu ZH, Henderson ACG, Huang Y (2006) Alkenone-based reconstruction of late-Holocene surface temperature and salinity changes in Lake Qinghai, China. Geophys Res Lett 33:L09707
Liu ZH, Henderson ACG, Huang YS (2008) Regional moisture source changes inferred from Late Holocene stable isotope records. Adv Atmos Sci 25:1021–1028
Lucas WJ, Berry JA (1985) Inorganic carbon transport in aquatic photosynthetic organisms. Physiol Plant 65:539–543
Mischke S, Kramer M, Zhang C, Shang H, Herzschuh U, Erzinger J (2008) Reduced early Holocene moisture availability in the Bayan Har Mountains, northeastern Tibetan Plateau, inferred from a multi-proxy lake record. Palaeogeogr Palaeoclimatol Palaeoecol 267:59–76
Morill C, Overpeck JT, Cole JE (2003) A synthesis of abrupt changes in the Asian summer monsoon since the last deglaciation. Holocene 13:465–476
Mügler I, Gleixner G, Mäusbacher R, Daut G, Schütt B, Berking J, Schwalb A, Schwark L, Xu B, Yao T, Zhu L, Yi C (2009) A multi-proxy approach to reconstruct hydrological changes and Holocene climate development of Nam Co, Central Tibet. J Paleolimn. doi 10.1007/s10933-009-9357-0
Papadimitrou S, Kennedy H, Kennedy DP, Borum J (2005) Seasonal and spatial variation in the organic carbon and nitrogen concentration and their stable isotopic composition in Zostera marina (Denmark). Limnol Oceanogr 50:1084–1095
Pease TK, Van Vleet ES, Barre JS, Dickins HD (1998) Simulated degradation of glyceryl ethers by hydrous and flash pyrolysis. Org Geochem 29:979–988
Peters KE, Walters CC, Moldowan JM (2005) The biomarker guide, volume 1 and 2: biomarkers and isotopes in the petroleum exploration and earth history. Cambridge University Press, Cambridge
Prins HBA, Elzenga JTM (1989) Bicarbonate utilization: function and mechanism. Aquat Bot 34:59–83
Radke M, Willsch H, Welte DH (1980) Preparative hydrocarbon group type determination by automated medium pressure liquid chromatography. Anal Chem 52:406–411
Reimer PJ, Baillie MGL, Bard E, Bayliss A, Beck JW, Bertrand CHJ, 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 G, Manning S, Bronk Ramsey C, Reimer RW, Plicht JVD, Weyhenmeyer CE (2004) IntCal04 terrestrial radiocarbon age calibration, 0–26 cal kyr BP. Radiocarbon 46:1029–1058
Risatti JB, Rowland SJ, Yon DA, Maxwell JR (1984) Stereochemical studies of acyclic isoprenoids-XII. Lipids of methanogenic bacteria and possible contributions to sediments. Org Geochem 6:93–103
Rohmer M, Bouvier-Nave P, Ourisson G (1984) Distribution of hopanoid triterpenes in prokaryotes. J Gen Microbiol 130:1137–1150
Rowland SJ, Robson JN (1990) The widespread occurrence of highly branched acyclic C20, C25 and C30 hydrocarbons in recent sediments and biota—a review. Mar Environ Res 30:191–216
Rowland SJ, Yon DA, Lewis CA, Maxwell JR (1985) Occurrence of 2,6,10-trimethyl-7-(3-methylbutyl) dodecane and related hydrocarbons in the green alga Enteromorpha prolifera and sediments. Org Geochem 8:207–213
Ruddiman WF, Kutzbach JE (1989) Forcing of Late Cenozoic Northern Hemisphere climate by plateau uplift in southern Asia and the America west. J Geophys Res 94:18409–18427
Schaefer H, Whiticar MJ (2008) Potential glacial-interglacial changes in stable carbon isotope ratios of methane sources and sink fractionation. Global Biogeochem Cycles 22:GB1001
Schouten S, van der Maarel MJEC, Huber R, Sinninghe Damsté JS (1997) 2, 6, 10, 15, 19-pentamethylicosenes in Methanolobus bombayensis, a marine methanogenic archaeon and Methanosarcina mazei. Org Geochem 26:409–414
Schouten S, Rijpstra WIC, Kok M, Hopmans EC, Summons RE, Volkman JK, Sinninghe-Damsté JS (2001) Molecular organic tracers of biogeochemical processes in a saline meromictic lake (Ace Lake). Geochim Cosmochim Acta 65:1629–1640
Shen J, Liu XQ, Wang SM, Matsumoto R (2005) Palaeoclimatic changes in the Qinghai Lake area during the last 18, 000 years. Quat Int 136:131–140
Sinninghe-Damsté J, Muyzer G, Abbas B, Rampen SW, Massé G, Allard WG, Belt ST, Robert JM, Rowland SJ, Moldowan JM, Barbanti SM, Fago FJ, Denisevich P, Dahl J, Trindade LAF, Schouten S (2004) The rise of the Rhizosolenid diatoms. Science 304:584–587
Street-Perrott FA, Ficken KJ, Huang YS, Eglinton G (2004) Late quaternary changes in carbon cycling on Mt. Kenya, East Africa: an overview of the delta C-13 record in lacustrine organic matter. Quat Sci Rev 23:861–879
Stumm W, Morgan JJ (1981) Aquatic chemistry: an introduction emphasizing chemical equilibria in natural waters, 2nd edn. Wiley, New York
Summons RE, Jahnke LJ, Roksandic Z (1994) Carbon isotopic fractionation in lipids from methanotrophic bacteria: relevance for interpretation of the geochemical record of biomarkers. Geochim Cosmochim Acta 58:2853–2863
Summons RE, Franzmann PD, Nichols PD (1998) Carbon isotopic fractionation associated with methylotrophic methanogenesis. Org Geochem 28:465–475
Thiel V, Peckmann J, Seifert R, Wehrung P, Reitner J, Michaelis W (1999) Highly isotopically depleted isoprenoids: molecular markers for ancient methane venting. Geochim Cosmochim Acta 63:3959–3966
Thompson LG (2000) Ice core evidence for climate change in the Tropics: implications for our future. Quat Sci Rev 19:19–35
Thompson LG, Yao T, Davis ME, Henderson KA, Mosley-Thompson E, Lin P, Beer J, Synal HA, Cole-Dai J, Bolzan JF (1997) Tropical climate instability: the last glacial cycle from a Qinghai-Tibetan ice core. Science 276:1821–1825
Uemura H, Ishiwatari R (1995) Identification of unusual 17β(H)-moret-22(29)-ene in lake sediments. Org Geochem 23:675–680
Venkatesan MI, Kaplan IR (1987) Organic geochemistry of Antarctic marine sediments, Part I. Bransfield Strait. Mar Chem 21:347–375
Volkman JK, Allen DI, Stevenson PL, Burton HR (1986) Bacterial and algal hydrocarbons in sediments from a saline Antarctic Lake, Ace Lake. Org Geochem 10:671–681
Wakeham SG (1990) Algal and bacterial hydrocarbons in particulate matter and interfacial sediment of the Cariaco Trench. Geochim Cosmochim Acta 54:1325–1336
Wang FB, Fan CY (1987) Climatic changes in the Qinghai-Xizang (Tibetan) region of China during the Holocene. Quat Res 28:50–60
Wang R, Zheng M (1998) Occurence and environmental significance of long-chain alkenones in Tibetan Zabuye Salt Lake, S.W. China. Int J Salt Lake Res 6:281–302
Wang R, Brassel SC, Scarpitta SC, Zheng MP, Zhang SC, Hayde PR, Muench LM (2004) Steroids in sediments from Zabuye Salt Lake, western Tibet: diagenetic, ecological or climatic signals? Org Geochem 35:157–168
Wang P, Clemens S, Beaufort L, Braconnot P, Ganssen G, Jian Z, Kershaw P, Sarthein M (2005) Evolution and variability of the Asian monsoon system: state of the art and outstanding issues. Quat Sci Rev 24:595–629
Whiticar MJ, Faber E, Schoell M (1986) Biogenic methane formation in marine and freshwater environments: CO2 reduction vs. acetate fermentation–Isotope evidence. Geochim Cosmochim Acta 50:693–709
Wilkes H, Ramrath A, Negendank JFW (1999) Organic geochemical evidence for environmental changes since 34, 000 yrs BP from Lago di Mezzano, central Italy. J Paleolimnol 22:349–365
Xu Y, Jaffé R, Wachnicka A, Gaiser EE (2006) Occurrence of C25 highly branched isoprenoids (HBIs) in Florida Bay: paleoenvironmental indicators of diatom-derived organic matter inputs. Org Geochem 37:847–859
Yon DA, Ryback G, Maxwell JR (1982) 2, 6, 10-trimethyl-7-(3 methylbutyl)dodecane, a novel sedimentary biological marker compound. Tetrahedron Lett 23:2143–2146
Zheng Y, Zhou W, Meyers PA, Xie S (2007) Lipid biomarkers in the Zoige-Hongyuan peat deposit: indicators of Holocene climate changes in West China. Org Geochem 38:1927–1940
Zhou J, Wang S, Yang G, Xiao H (2007) Younger Dryas event and cold events in early-mid Holocene: record from the sediment of Erhai Lake. Adv Clim Change Res 3(Suppl):41–44
Zhu L, Wu Y, Wang J, Lin X, Ju J, Xie M, Li M, Mäusbacher R, Schwalb A, Daut G (2008) Environmental changes since 8.4 ka reflected in the lacustrine core sediments from Nam Co, central Tibetan plateau, China. Holocene 18:831–839
Acknowledgments
We thank Andrea Vieth, Kai Mangelsdorf and Ann-Kathrin Scherf for helpful comments concerning the interpretation of mass spectra and δ13C curves. We thank Martin Zalkow and the lab staff of the Organic Geochemistry section of the GFZ (Anke Sobotta, Cornelia Karger, Kristin Günther, Michael Gabriel and Doreen Noack) for assistance during preparation and analysis of the samples. Further, we acknowledge two anonymous reviewers for their constructive comments on the manuscript. Funding was provided by the German Science Foundation (DFG).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Aichner, B., Wilkes, H., Herzschuh, U. et al. Biomarker and compound-specific δ13C evidence for changing environmental conditions and carbon limitation at Lake Koucha, eastern Tibetan Plateau. J Paleolimnol 43, 873–899 (2010). https://doi.org/10.1007/s10933-009-9375-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10933-009-9375-y