Characterisation of sedimentary organic matter from three south-eastern Australian estuaries using solid-state 13 C-NMR techniques
C. J. Golding A C , R. J. Smernik B and G. F. Birch AA School of Geosciences, The University of Sydney, NSW 2006, Australia.
B Soil and Land Systems, School of Earth and Environmental Sciences, The University of Adelaide, Waite Campus, Urrbrae, SA 5064, Australia.
C Corresponding author. Email: cgolding@geosci.usyd.edu.au
Marine and Freshwater Research 55(3) 285-293 https://doi.org/10.1071/MF03167
Submitted: 23 September 2003 Accepted: 19 March 2004 Published: 19 May 2004
Abstract
Solid state 13C-nuclear magnetic resonance (NMR) spectroscopy was used to characterise sedimentary organic matter sampled from three estuaries on the central New South Wales coast (Australia). Cross polarisation (CP) and Bloch decay (BD) experiments were used to determine the chemical composition of the samples. These experiments indicated that, although the natural organic matter is predominately terrestrial in origin, the proportion of carbon existing as aromatic carbon, distinctive of vascular plants, decreases towards the mouth of the estuaries. This suggests that the relative contribution of terrestrial and marine source material largely defines the character of estuarine organic matter. Substantial amounts of charcoal were identified in sedimentary organic matter close to recent bushfire activity. Proton-spin relaxation editing (PSRE) was used to probe the physical structure of the sedimentary organic matter at the sub-micron scale. This technique showed that the organic matter was heterogeneous, providing support for a popular model of sedimentary organic matter structure. However, detailed interpretation of the domain structure of the organic matter was hindered by the presence of multiple components from both terrestrial and marine sources.
Extra keywords: Bloch decay; cross polarisation; proton-spin relaxation editing.
Acknowledgments
This research was completed while G. F. B. was in receipt of an ARC Linkage Grant: we gratefully acknowledge this financial assistance. Estuary maps were provided by Andrew Heap of Geoscience Australia. Thanks to Tom Savage and Kevin Davies from the University of Sydney for their valuable advice.
Alexander, M. (2000). Aging, bioavailability and overestimation of risk from environmental pollutants. Environmental Science & Technology 34, 4259–4265.
| Crossref | GoogleScholarGoogle Scholar |
APHA (1998). (American Public Health Association: Washington, DC, USA.)
Birch, G. F. , and Taylor, S. E. (1999). Source of heavy metals in sediments of Port Jackson estuary, Australia. The Science of the Total Environment 227, 123–138.
| Crossref | GoogleScholarGoogle Scholar |
Birch, G. F. , and Taylor, S. E. (2000). The distribution and possible sources of organochlorine residues in sediments of a large urban estuary, Port Jackson, Sydney. Australian Journal of Earth Sciences 47, 749–756.
| Crossref | GoogleScholarGoogle Scholar |
Birch, G. F. , Ingelton, T. , and Taylor, S. E. (1997). Environmental implications of dredging in the world's second largest coal exporting harbour, Port Hunter, Australia. Journal of Marine Environmental Engineering 4, 133–145.
Birch, G. F. , Shotter, N. , and Steetsel, P. (1998). The environmental status of Hawkesbury River sediments. Australian Geographical Studies 36, 37–57.
| Crossref | GoogleScholarGoogle Scholar |
Chen, W. , Kan, A. T. , Fu, G. , and Tomson, M. B. (2000). Factors affecting the release of hydrophobic organic contaminants from natural sediments. Environmental Toxicology and Chemistry 19, 2401–2408.
Chen, W. , Kan, A. T. , and Tomson, M. B. (2000). Irreversible adsorption of chlorinated benzenes to natural sediments: implications for sediment quality criteria. Environmental Science & Technology 34, 385–392.
| Crossref | GoogleScholarGoogle Scholar |
Chiou, C. T. , and Kile, D. E. (1998). Deviations from sorption linearity on soils of polar and nonpolar organic compounds at low relative concentrations. Environmental Science & Technology 32, 338–343.
| Crossref | GoogleScholarGoogle Scholar |
Cornelissen, G. , Hassel, K. A. , van Noort, P. C. M. , Kraaij, R. , van Ekeren, P. J. , Dijkema, C. , de Jager, P. A. , and Govers, H. A. J. (2000). Slow desorption of PCBs and chlorobenzenes from soils and sediments: relations with sorbent and sorbate characteristics. Environmental Pollution 108, 69–80.
| Crossref | GoogleScholarGoogle Scholar | PubMed |
de Leeuw, J. W. and Largeau, C. (1993). A review of macromolecular organic compounds that comprise living organisms and their role in kerogen, coal and petroleum formation. In (Eds. M. H. Engle and S. Macko) pp. 23–72. (Plenum Press: New York, USA.)
Di Toro, D. M. , Zarba, C. A. , Hansen, D. J. , Berry, W. J. , Swartz, R. C. , Cowan, C. E. , Pavlou, S. P. , Allen, H. E. , Thomas, N. A. , and Paquin, P. R. (1991). Technical basis for establishing sediment quality criteria for nonionic organic chemicals using equilibrium partitioning. Environmental Toxicology and Chemistry 10, 1541–1583.
Emerson, S. , Stump, C. , Grootes, P. M. , Stuiver, M. , Farwell, G. W. , and Schmidt, F. H. (1987). Estimates of degradable organic carbon in deep-sea sediments from 14C concentrations. Nature 329, 51–53.
| Crossref | GoogleScholarGoogle Scholar |
Gelin, F. , Boogers, I. , Noordeloos, A. A. M. , Sinninghe Damste, J. S. , Hatcher, P. G. , and de Leeuw, J. W. (1996). Novel, resistant microalgal polyethers: an important sink of organic carbon in the marine environment? Geochimica et Cosmochimica Acta 60, 1275–1280.
| Crossref | GoogleScholarGoogle Scholar |
Gelinas, Y. , Baldock, J. A. , and Hedges, J. I. (2001). Demineralisation of marine and freshwater sediments for CP/MAS 13C-NMR analysis. Organic Geochemistry 32, 677–693.
| Crossref | GoogleScholarGoogle Scholar |
Gelinas, Y. , Baldock, J. A. , and Hedges, J. I. (2001). Organic carbon composition of marine sediments: effect of oxygen exposure on oil generation potential. Science 294, 145–148.
| Crossref | GoogleScholarGoogle Scholar | PubMed |
Hatcher, P. G. , and Clifford, D. J. (1997). The organic geochemistry of coal: from plant materials to coal. Organic Geochemistry 27, 251–274.
| Crossref | GoogleScholarGoogle Scholar |
Hedges, J. I. , and Keil, R. G. (1995). Sedimentary organic matter preservation: an assessment and speculative synthesis. Marine Chemistry 49, 81–115.
| Crossref | GoogleScholarGoogle Scholar |
Hedges, J. I. , and Keil, R. G. (1999). Organic geochemical perspectives on estuarine processes: sorption reactions and consequences. Marine Chemistry 65, 55–65.
| Crossref | GoogleScholarGoogle Scholar |
Hedges, J. I. , Keil, R. G. , and Benner, R. (1997). What happens to terrestrial organic matter in the ocean? Organic Geochemistry 27, 195–212.
| Crossref | GoogleScholarGoogle Scholar |
Hedges, J. I. , Eglington, G. , Hatcher, P. G. , Kirchman, D. L. , and Arnosti, C. , et al. (2000). The molecularly-uncharacterized component of nonliving organic matter in natural environments. Organic Geochemistry 31, 945–958.
| Crossref | GoogleScholarGoogle Scholar |
Hedges, J. I. , Baldock, J. A. , Gelinas, Y. , Lee, C. , Peterson, M. , and Wakeham, S. G. (2001). Evidence for non-selective preservation of organic matter in sinking marine particles. Nature 409, 801–804.
| Crossref | GoogleScholarGoogle Scholar | PubMed |
Lueking, A. D. , Huang, W. , Soderstrom-Schwarz, S. , Kim, M. , and Weber, W. J. J. (2000). Relationship of soil organic matter characteristics to organic contaminant sequestration and bioavailability. Journal of Environmental Quality 29, 317–323.
Luthy, R. G. , Aiken, G. R. , Brusseau, M. L. , Cunningham, S. D. , Gschwend, P. M. , Pignatello, J. J. , Reinhard, M. , Traina, S. J. , Weber, W. J. J. , and Westall, J. C. (1997). Sequestration of hydrophobic organic contaminants by geosorbents. Environmental Science & Technology 31, 3341–3347.
| Crossref | GoogleScholarGoogle Scholar |
Masiello, C. A. , and Druffel, E. R. M. (1998). Black carbon in deep-sea sediments. Science 280, 1911–1913.
| Crossref | GoogleScholarGoogle Scholar | PubMed |
Mathers, N. J. , Mao, X. A. , Xu, Z. H. , Saffigna, P. G. , Berners-Price, S. J. , and Perera, M. C. S. (2000). Recent advances in the application of 13C and 15N NMR spectroscopy to soil organic matter studies. Australian Journal of Soil Research 38, 769–787.
| Crossref | GoogleScholarGoogle Scholar |
McCready, S. , Slee, D. , Birch, G. F. , and Taylor, S. E. (2000). The distribution of polycyclic aromatic hydrocarbons in surficial sediments of Sydney Harbour, Australia. Marine Pollution Bulletin 40, 999–1006.
| Crossref | GoogleScholarGoogle Scholar |
Perminova, I. V. , Grechishcheva, N. Y. , and Petrosyan, V. S. (1999). Relationships between structure and binding affinity of humic substances for polycyclic aromatic hydrocarbons: relevance of molecular descriptors. Environmental Science & Technology 33, 3781–3787.
| Crossref | GoogleScholarGoogle Scholar |
Pignatello, J. J. , and Xing, B. (1996). Mechanisms of slow sorption of organic compounds to natural particles. Environmental Science & Technology 30, 1–11.
| Crossref | GoogleScholarGoogle Scholar |
Randall, E. W. , Mahieu, N. , and Ivanova, G. I. (1997). NMR studies of soil, soil organic matter and nutrients: spectroscopy and imaging. Geoderma 80, 307–325.
| Crossref | GoogleScholarGoogle Scholar |
Roy, P. S. (1984). New South Wales estuaries: their origin and evolution. In (Ed B. G. Thom.) pp. 99–121. (Academic Press: Sydney, Australia.)
Salloum, M. J. , Chefetz, B. , and Hatcher, P. G. (2002). Phenanthrene sorption by aliphatic-rich natural organic matter. Environmental Science & Technology 36, 1953–1958.
| Crossref | GoogleScholarGoogle Scholar | PubMed |
Sarmiento, J. L. , and Toggweiler, J. R. (1984). A new model for the role of the oceans in determining atmospheric pCO2. Nature 308, 621–624.
Schmidt, M. W. I. , Skjemstad, J. O. , and Jäger, C. (2002). Carbon isotope geochemistry and nanomorphology of soil black carbon: Black chernozemic soils in central Europe originate from ancient biomass burning. Global Biogeochemical Cycles 16, 1123–1130.
| Crossref | GoogleScholarGoogle Scholar |
Skjemstad, J. O. , Clarke, P. , Taylor, J. A. , Oades, J. M. , and Newman, R. H. (1994). The removal of magnetic materials from surface soils. A solid state 13C CP/MAS NMR study. Australian Journal of Soil Research 32, 1215–1229.
Skjemstad, J. O. , Clarke, P. , Taylor, J. A. , Oades, J. M. , and McClure, S. G. (1996). The chemistry and nature of protected carbon in soil. Australian Journal of Soil Research 34, 251–271.
Smernik, R. J. , and Oades, J. M. (1999). Effects of added paramagnetic ions on the 13C CP/MAS NMR spectrum of a de-ashed soil. Geoderma 89, 219–248.
| Crossref | GoogleScholarGoogle Scholar |
Smernik, R. J. , and Oades, J. M. (2000). The use of spin counting for determining quantitation in solid state 13C-NMR spectra of natural organic matter: 1. Model systems and the effects of paramagnetic impurities. Geoderma 96, 101–129.
| Crossref | GoogleScholarGoogle Scholar |
Smernik, R. J. , and Oades, J. M. (2000). The use of spin-counting for determining quantitation in solid state 13C-NMR spectra of natural organic matter: 2. HF-treated soil fractions. Geoderma 96, 159–171.
| Crossref | GoogleScholarGoogle Scholar |
Smernik, R. J. , Baldock, J. A. , and Oades, J. M. (2000). Effect of paramagnetic cations on solid state 13C nuclear magnetic resonance spectra of natural organic materials. Communications in Soil Science and Plant Analysis 31, 3011–3026.
Smernik, R. J. , Skjemstad, J. O. , and Oades, J. M. (2000). Virtual fractionation of charcoal from soil organic matter using solid state 13C-NMR spectral editing. Australian Journal of Soil Research 38, 665–683.
Smernik, R. J. , Baldock, J. A. , Oades, J. M. , and Whittaker, A. K. (2002). Determination of T1ρH relaxation rates in charred and uncharred wood and consequences for NMR quantitation. Solid State Nuclear Magnetic Resonance 22, 50–70.
| Crossref | GoogleScholarGoogle Scholar | PubMed |
ten Hulscher, D. T. E. M. , van Noort, P. C. M. , and van der Velde, L. E. (1997). Equilibrium partitioning theory overestimates chlorobenzene concentrations in sediment porewater from Lake Ketelmeer, The Netherlands. Chemosphere 35, 2331–2344.
| Crossref | GoogleScholarGoogle Scholar |
Thornton, S. F. , and McManus, J. (1994). Application of organic carbon and nitrogen stable isotope and C/N ratios as source indicators of organic matter provenance in estuarine systems: Evidence from the Tay estuary, Scotland. Estuarine, Coastal and Shelf Science 38, 219–233.
| Crossref | GoogleScholarGoogle Scholar |
Weber, W. J. J. , Kim, S. H. , and Johnson, M. D. (2002). A distributed reactivity model for sorption by soils and sediments. 15. High-concentration co-contaminant effects on phenanthrene sorption and desorption. Environmental Science & Technology 36, 3625–3634.
| Crossref | GoogleScholarGoogle Scholar | PubMed |
Wilson, M. A. (1987). (Pergamon Press: Oxford, UK.)
Young, T. M. , and Weber, W. J. J. (1995). A distributed reactivity model for sorption by soils and sediments. 3. Effects of diagenetic processes on sorption energetics. Environmental Science & Technology 29, 92–97.
Zann, L. P. (1996). The State of the Marine Environment Report for Australia: the process, major findings and perspectives. Ocean and Coastal Management 33, 63–86.
| Crossref | GoogleScholarGoogle Scholar |