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Molecular fingerprinting of wetland organic matter using pyrolysis-GC/MS: an example from the southern Cape coastline of South Africa

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Abstract

Pyrolysis–gas chromatography mass spectrometry (py-GC/MS) allows the characterisation of complex macromolecular organic matter. In lakes and wetlands this can potentially be used to assess the preservation/diagenesis and provenance of sediment organic matter. It can complement palaeoenvironmental investigations utilising ‘bulk’ sediment variables such as total organic carbon (TOC) and TOC/total nitrogen ratios. We applied py-GC/MS analyses to a ~32,000-year sediment record from the southern Cape coastline of South Africa. We used the results to evaluate the sources and extent of degradation of organic matter in this semi-arid environment. Marked down-core changes in the relative abundance of multiple pyrolysis products were observed. Correspondence analysis revealed that the major driver of this down-core variability in OM composition was selective preservation/degradation. Samples comprising highly degraded OM are primarily confined to the lower half of the core, older than ~12,000 years, and are characterised by suites of low-molecular-weight aromatic pyrolysis products. Samples rich in organic matter, e.g. surface sediments, are characterised by products derived from fresh emergent or terrestrial vegetation, which include lignin monomers, plant-derived fatty acids and long-chain n-alkanes. Pyrolysates from the late glacial-early Holocene period, approximately mid-way down the core are characterised by distinct suites of long-chain n-alkene/n-alkane doublets, which may reflect the selective preservation of recalcitrant aliphatic macromolecules and/or enhanced inputs of the algal macromolecule algaenan/polymerised algal lipids. Increased TOC, lower δ13C and increased abundance of more labile lignin and fatty acid products at the same depths suggest this period was associated with increased lake primary productivity and enhanced inputs of terrestrial OM. TOC is the only ‘bulk’ parameter correlated with the correspondence analysis axes extracted from the py-GC/MS data. Distinct fluctuations in TOC/total nitrogen ratio are not explained by variation in organo-nitrogen pyrolysis products. Notwithstanding, the study suggests that py-GC/MS has potential to complement palaeolimnological investigations, particularly in regions such as southern Africa, where other paleoenvironmental proxy variables in sediments may be lacking or equivocal.

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References

  • Augris N, Balesdent J, Mariotti A, Derenne S, Largeau C (1998) Structure and origin of insoluble and non-hydrolyzable, aliphatic organic matter in a forest soil. Org Geochem 28:119–124

    Article  Google Scholar 

  • Blokker P, Schouten S, Van den Ende H, de Leeuw JW, Hatcher PG, Sinninghe-Damsté JS (1998) Chemical structure of algaenans from the fresh water algae Tetraedron minimum, Scenedesmus communis and Pediastrum boryanum. Org Geochem 29:1453–1468

    Article  Google Scholar 

  • Boerjan W, Ralph J, Baucher M (2003) Lignin biosynthesis. Annu Rev Plant Biol 54:519–546

    Article  Google Scholar 

  • Boom A, Sinninghe-Damsté JS, de Leeuw JW (2005) Cutan, a common aliphatic biopolymer in cuticles of drought-adapted plants. Org Geochem 36:595–601

    Article  Google Scholar 

  • Bourdon S, Laggoun-Défarge F, Disnar DR, Maman O, Guillet B, Derenne S, Largeau C (2000) Organic matter sources and early diagenetic degradation in a tropical peaty marsh (Tritrivakely, Madagascar). Implications for environmental reconstruction during the Sub-Atlantic. Org Geochem 31:421–438

    Article  Google Scholar 

  • Bracewell JM, Robertson GW (1984) Quantitative comparison of the nitrogen-containing pyrolysis products and amino acid composition of soil humic acids. J Anal Appl Pyrolysis 6:19–29

    Article  Google Scholar 

  • Buurman P, van Bergen PF, Jongmans AG, Meijer EL, Duran B, van Lagen B (2005) Spatial and temporal variation in podzel organic matter studied by pyrolysis-gas chromatography/mass spectrometry and micromorphology. Eur J Soil Biol 56:253–270

    Google Scholar 

  • Buurman P, Schellekens J, Fritze H, Nierop KGJ (2007) Selective depletion of organic matter in mottled podzol horizons. Soil Biol Biochem 39:607–621

    Article  Google Scholar 

  • Carr AS, Thomas DSG, Bateman MD, Meadows ME, Chase BM (2006) Late Quaternary palaeoenvironments of the winter-rainfall zone of southern Africa: palynological and sedimentological evidence from the Agulhas Plain. Palaeogeogr Palaeoclimatol Palaeoecol 239:147–165

    Article  Google Scholar 

  • Chase BM, Meadows ME (2007) Late Quaternary dynamics of southern Africa’s winter rainfall zone. Earth Sci Rev 84:103–138

    Article  Google Scholar 

  • Das SK, Routh J, Roychoudhury AN, Val Klump J (2008) Elemental (C, N, H and P) and stable isotope (δ15N and δ13C) signatures in sediments from Zeekoevlei, South Africa: a record of human intervention in the lake. J Palaeolimnol 36:349–360

    Article  Google Scholar 

  • de Leeuw JW, Versteegh GJM, van Bergen PF (2006) Biomacromolecules of algae and plants and their fossil analogues. Plant Ecol 182:209–233

    Google Scholar 

  • Deacon HJ, Deacon J, Scholtz A, Thackeray JF, Brink JS, Vogel JC (1984) Correlation of palaeoenvironmental data from the Late Pleistocene and Holocene deposits at Boomplaas cave, southern Cape. In: Vogel JC (ed) Late Cainozoic Palaeoenvironments of the Southern Hemisphere. AA Balkema, Rotterdam, pp 339–352

    Google Scholar 

  • Fuhrmann A, Mingram J, Lücke A, Lu H, Horsfield B, Liu J, Negendank JFW, Schleser GH, Wilkes H (2003) Variations in organic matter composition in sediments from Lake Huguang Maar (Huguangyan), south China during the last 68 ka: Implications for environmental and climatic change. Org Geochem 34:1497–1515

    Article  Google Scholar 

  • Fuhrmann A, Fischer T, Lücke A, Brauer A, Zolitschka B, Horsfield B, Negendank JFW, Schleser GH, Wilkes H (2004) Late Quaternary environmental and climatic changes in central Europe as inferred from the composition of organic matter in annually laminated maar lake sediments. Geochem Geophys Geosyst 5, Article Number: Q11015

  • Huang Y, Stankiewicz BA, Eglinton G, Snape CE, Evans B, Latter PM, Ineson P (1998) Monitoring biomacromolecular degradation of Calluna vulgaris in a 23 year field experiment using solid state 13C-NMR and pyrolysis GC/MS. Soil Biol Biochem 30:1517–1528

    Article  Google Scholar 

  • Irving SJ (1998) Late Quaternary palaeoenvironments at Vankervelsvlei, near Knysna, South Africa. Unpublished MSc thesis, University of Cape Town

  • Irving SJ, Meadows ME (1997) Radiocarbon chronology and organic matter accumulation at Vankervelsvlei, near Knysna, South Africa. S Afr Geogr J 79:101–105

    Google Scholar 

  • Ishiwatari M, Ishiwatari R, Sakashita H, Tatsumi T, Tominaga H (1991) Pyrolysis of chlorophyll-a after preliminary heating at a moderate temperature: implications for the origins of Prist-1-ene on kerogen pyrolysis. J Anal Appl Pyrolysis 18:207–218

    Article  Google Scholar 

  • Kaal J, Baldock JA, Buurman P, Nierop KGJ, Pontevedra-Pombol X, Martínez-Cortizas AM (2007) Evaluating pyrolysis-GC/MS and 13C CPMAS NMR in conjunction with a molecular mixing model of the Penido Vello peat deposit, NW Spain. Org Geochem 38:1097–1111

    Article  Google Scholar 

  • Kaal J, Martinez-Cortizas A, Nierop KGJ (2009) Characterisation of aged charcoal using a coil probe pyrolysis-GC/MS method optimised for black carbon. J Anal Appl Pyrolysis 85:408–416

    Article  Google Scholar 

  • Kögel-Knaber I (2002) The macromolecular organic composition of plant and microbial residues as inputs to soil organic matter. Soil Biol Biochem 34:139–162

    Article  Google Scholar 

  • Lamb AL, Leng MJ, Mohammed MU, Lamb HF (2004) Holocene climate and vegetation change in the Main Ethiopian Rift Valley, inferred from the composition (C/N and δ13C) of lacustrine organic matter. Quat Sci Rev 23:881–891

    Article  Google Scholar 

  • Lanesky DE, Logan BW, Brown RG, Hine AC (1979) A new approach to portable vibracoring underwater and on land. J Sediment Petrol 49:654–657

    Google Scholar 

  • Liu W, Huang Y (2008) Reconstructing in situ vegetation dynamics using carbon isotopic composition of biopolymeric residues in the central Chinese Loess Plateau. Chem Geol 249:348–356

    Article  Google Scholar 

  • Martin ARH (1968) Pollen analysis of Groenvlei lake catchments, Knysna. Rev Palaeobot Palynol 7:107–144

    Article  Google Scholar 

  • McCormac FG, Hogg AG, Blackwell PG, Buck CE, Higham TFG, Reimer PJ (2004) SHCal04 Southern Hemisphere calibration, 0–11.0 cal kyr BP. Radiocarbon 46:1087–1092

    Google Scholar 

  • Meyers PA (1997) Organic geochemical proxies of paleoceanographic, paleolimnologic, and paleoclimatic processes. Org Geochem 27:213–250

    Google Scholar 

  • Meyers PA, Lallier-Vergés E (1999) Lacustrine sedimentary organic matter records of Late Quaternary palaeoclimates. J Palaeolimnol 21:345–372

    Article  Google Scholar 

  • Nguyen RT, Harvey HR, Zang X, van Heemst JDH, Hetényi M, Hatcher PG (2003) Preservation of algaenan and proteinaceous material during the oxic decay of Brotryococcus braunii as revealed by pyrolysis-gas chromatography/mass spectrometry and 13C NMR spectroscopy. Org Geochem 34:483–497

    Article  Google Scholar 

  • Nierop KGJ (1998) Origin of aliphatic compounds in a forest soil. Org Geochem 29:1009–1016

    Article  Google Scholar 

  • Nierop KGJ, Pulleman MM, Marinissen JCY (2001) Management induced organic matter differentiation in grassland and arable soil: a study using pyrolysis techniques. Soil Biol Biochem 33:755–764

    Article  Google Scholar 

  • Rebelo AG, Cowling RM, Campbell BM, Meadows M (1991) Plant communities of the Riversdale Plain. S Afr J Bot 57:10–28

    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 TJ, 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 51:1111–1150

    Google Scholar 

  • Roberts D, Murray-Wallace CV, Bateman MD, Carr AS, Holmes PJ (2008) Fossil elephant trackways, sedimentation and diagenesis in OSL/AAR-dated Late Quaternary coastal aeolianites: Still Bay, South Africa. Palaeogeogr Palaeoclimatol Palaeoecol 257:261–279

    Article  Google Scholar 

  • Saiz-Jimenez C, de Leeuw JW (1987) Chemical characterization of soil organic matter fractions by analytical pyrolysis–gas chromatography–mass spectrometry. J Anal Appl Pyrolysis 9:99–119

    Article  Google Scholar 

  • Saiz-Jimenez C, Boon JJ, Hedges JI, Hessels JKC, de Leeuw JW (1987) Chemical characterisation of recent and buried woods by analytical pyrolysis: comparison of pyrolysis data with 13C NMR and wet chemical data. J Anal Appl Pyrolysis 11:437–450

    Article  Google Scholar 

  • Schellekens J, Buurman P, Pontevedra-Pombal X (2009) Selecting parameters for the environmental interpretation of peat molecular chemistry. Org Geochem 40:678–691

    Article  Google Scholar 

  • Scholtz A (1986) Palynological and Palaeobotanical Studies in the Southern Cape. Unpublished MA thesis, University of Stellenbosch

  • Stuiver M, Reimer PJ (1993) Extended 14C data base and revised CALIB 3.0 14C age calibration program. Radiocarbon 35:215–230 (version 6.0)

    Google Scholar 

  • Tegelaar EW, Hollman G, Vandervegt P, De Leeuw JW, Holloway PJ (1995) Chemical characterization of the periderm tissue of some angiosperm species—recognition of an insoluble, nonhydrolyzable, aliphatic biomacromolecule (suberan). Org Geochem 23:239–251

    Article  Google Scholar 

  • ter Braak CJF (1995) Ordination. In: Jongman RHG, ter Braak CJF, van Tongeren OFR (eds) Data analysis in community and landscape ecology. Cambridge University Press, Cambridge, pp 91–173

    Chapter  Google Scholar 

  • Thevenot M, Dignac M-F, Rumpel C (2010) Fate of lignin in soils: a review. Soil Biol Biochem 42:1200–1211

    Article  Google Scholar 

  • van Bergen PF, Bull ID, Poulton PR, Evershed RP (1997) Organic geochemical studies of soils from the Rothamsted Classical Experiments I. Total lipids, solvent insoluble residues and humic acids from Broadbalk Wilderness. Org Geochem 26:117–135

    Article  Google Scholar 

  • van Smeerdijk DG, Boon JJ (1987) Characterisation of subfossil Sphagnum leaves, rootlets of ericaceae and their peat pyrolysis-high resolution gas chromatography mass spectrometry. J Anal Appl Pyrolysis 11:377–402

    Article  Google Scholar 

  • Vancampenhout K, Wouters K, Caus A, Buurman P, Swennen R, Deckers J (2008) Fingerprinting of soil organic matter as a proxy for assessing climate and vegetation changes in last interglacial palaeosols (Veldwezelt, Belgium). Quat Res 69:145–162

    Article  Google Scholar 

  • Vancampenhout K, Wouters K, De Vos B, Buurman P, Swennen R, Deckers J (2009) Differences in chemical composition of soil organic matter in natural ecosystems from different climatic regimes—A pyrolysis-GC/MS study. Soil Biol Biochem 41:568–579

    Article  Google Scholar 

  • Verde JR, Buurman P, Martínez-Cortizas A, Macías F, Arbestain MC (2008) NaOH-extractable organic matter of andic soils from Galicia (NW Spain) under different land use regimes: a pyrolysis GC/MS study. Eur J Soil Sci 59:1096–1110

    Article  Google Scholar 

  • Versteegh GJM, Blokker P, Wood GD, Collinson ME, Sinninghe-Damsté JS, de Leeuw JW (2004) An example of oxidative polymerisation of unsaturated fatty acids as a preservation pathway for dinoflagellate organic matter. Org Geochem 35:1129–1139

    Article  Google Scholar 

  • Zang X, Hatcher PG (2002) A py-GC-MS and NMR spectroscopy study of organic nitrogen in Mangrove Lake sediments. Org Geochem 33:201–211

    Article  Google Scholar 

  • Zonneveld KAF, Versteegh GJM, Kasten S, Eglinton TI, Emeis K-C, Huguet C, Koch BP, de Lange GJ, de Leeuw JW, Middelburg JJ, Mollenhauer G, Prahl FG, Rethemeyer J, Wakeham SG (2010) Selective preservation of organic matter in marine environments; processes and impact on the sedimentary record. Biogeosci 7:483–511

    Article  Google Scholar 

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Acknowledgments

We thank Guy Gardener for access to the Rietvlei site and Professor Mike Meadows for use of the vibracorer. ASC thanks the Quaternary Research Association and the University of Leicester for funding the fieldwork associated with this project. The University of Leicester is also thanked for a research sabbatical allocated to ASC, which allowed this work to be completed. ZER is supported by the Leverhulme Trust (Grant F/00 212/AF awarded to ASC). Two reviewers are thanked for very constructive comments on an earlier version of this paper.

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Authors and Affiliations

  1. Department of Geography, University of Leicester, Leicester, UK

    Andrew S. Carr, Arnoud Boom & Zoë E. Roberts

  2. Department of Archaeology, History, Cultural Studies and Religion, University of Bergen, 5020, Bergen, Norway

    Brian M. Chase

  3. Council for Geoscience, Cape Town, South Africa

    David L. Roberts

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  1. Andrew S. Carr
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Correspondence to Andrew S. Carr.

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Carr, A.S., Boom, A., Chase, B.M. et al. Molecular fingerprinting of wetland organic matter using pyrolysis-GC/MS: an example from the southern Cape coastline of South Africa. J Paleolimnol 44, 947–961 (2010). https://doi.org/10.1007/s10933-010-9466-9

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