Biogeosciences www.biogeosciences.net 1726-4170 1726-4189 7 2 2010 10.5194/bg-7-483-2010 http://www.biogeosciences.net/7/483/2010/ http://www.biogeosciences.net/7/483/2010/bg-7-483-2010.html http://www.biogeosciences.net/7/483/2010/bg-7-483-2010.pdf 483 511 2010-02-05 Selective preservation of organic matter in marine environments; processes and impact on the sedimentary record K. A. F. Zonneveld G. J. M. Versteegh versteegh@uni-bremen.de S. Kasten T. I. Eglinton K.-C. Emeis C. Huguet B. P. Koch G. J. de Lange J. W. de Leeuw J. J. Middelburg G. Mollenhauer F. G. Prahl J. Rethemeyer S. G. Wakeham Fachbereich 5 – Geowissenschaften, Postfach 330440, 27412 Bremen, Germany Alfred Wegener Institute for Polar and Marine Research, Am Handelshafen 12, 27570 Bremerhaven, Germany Woods Hole Oceanographic Institution, Fye 111, MS#4, Woods Hole, Ma. 02543, USA Zentrum für Meeres- und Klimaforschung, Universität Hamburg, Bundesstraße 55, 20146 Hamburg, Germany University of Washington, School of Oceanography, P.O. Box 355351, Seattle, WA 98195, USA Royal Netherlands Institute for Sea Research, P.O. Box 59, 1790AB, Den Burg, The Netherlands Geochemistry, Faculty of Geosciences, Utrecht University P.O. Box 80.021, 3508 TA Utrecht, The Netherlands Institute of Environmental Biology, Faculty of Science, Utrecht University, The Netherlands Netherlands Institute of Ecology, Centre for Estuarine and Marine Ecology, P.O. Box 140, 4400 AC Yerseke, The Netherlands College of Oceanic and Atmospheric Sciences, COAS Administration Building 104, Oregon State University, Corvallis, OR 97331-5503, USA Skidaway Institute of Oceanography, 10 Ocean Science Circle, Savannah, GA 31411, USA The present paper is the result of a workshop sponsored by the DFG Research Center/Cluster of Excellence MARUM "The Ocean in the Earth System", the International Graduate College EUROPROX, and the Alfred Wegener Institute for Polar and Marine Research. The workshop brought together specialists on organic matter degradation and on proxy-based environmental reconstruction. The paper deals with the main theme of the workshop, understanding the impact of selective degradation/preservation of organic matter (OM) in marine sediments on the interpretation of the fossil record. Special attention is paid to (A) the influence of the molecular composition of OM in relation to the biological and physical depositional environment, including new methods for determining complex organic biomolecules, (B) the impact of selective OM preservation on the interpretation of proxies for marine palaeoceanographic and palaeoclimatic reconstruction, and (C) past marine productivity and selective preservation in sediments. <br><br> It appears that most of the factors influencing OM preservation have been identified, but many of the mechanisms by which they operate are partly, or even fragmentarily, understood. Some factors have not even been taken carefully into consideration. This incomplete understanding of OM breakdown hampers proper assessment of the present and past carbon cycle as well as the interpretation of OM based proxies and proxies affected by OM breakdown. <br><br> To arrive at better proxy-based reconstructions "deformation functions" are needed, taking into account the transport and diagenesis-related molecular and atomic modifications following proxy formation. <br><br> Some emerging proxies for OM degradation may shed light on such deformation functions. The use of palynomorph concentrations and selective changes in assemblage composition as models for production and preservation of OM may correct for bias due to selective degradation. Such quantitative assessment of OM degradation may lead to more accurate reconstruction of past productivity and bottom water oxygenation. <br><br> Given the cost and effort associated with programs to recover sediment cores for paleoclimatological studies, as well as with generating proxy records, it would seem wise to develop a detailed sedimentological and diagenetic context for interpretation of these records. With respect to the latter, parallel acquisition of data that inform on the fidelity of the proxy signatures and reveal potential diagenetic biases would be of clear value. Aller, R. C.: Transport and reactions in the bioirrigated zone, in: The Benthic Boundary Layer, edited by: Boudreau, B. P. and Jørgensen, B. B., Oxford University Press, Oxford, 269–301, 2001. Aller, R. C. and Blair, N. E.: Carbon remineralization in the Amazon-Guianas tropical mobile mudbelt: A sedimentary incinerator, Cont. Shelf Res., 26(17–18), 2241–2259, 2006. Altabet, M. A.: Constraints on oceanic N balance/imbalance from sedimentary $^15$N records, Biogeosciences, 4, 75–86, 2007. Altabet, M. A. and Francois, R.: The use of nitrogen isotopic ratio for reconstruction of past changes in surface ocean nutrient utilization, in: Carbon Cycling in the Glacial Ocean: Constraints on the Ocean's Role in Global Change, edited by: Zahn, R., Pedersen, T. F., Kaminski, M. A., and Labeyrie, L., Springer, Berlin, 281–306, 1994. Altabet, M. A., Higginson, M. J. and Murrey, D. W.: The effect of millennial-scale changes in Arabian Sea denitrification on atmospheric CO₂, Nature, 415, 159–162, 2002. Arnarson, T. S. and Keil, R. G.: Organic-mineral interactions in marine sediments studied using density fractionation and X-ray photoelectron spectroscopy, Org. Geochem. 32, 1401–1415, 2001. Arnarson, T. S. and Keil, R. G.: Influence of organic-mineral aggregates on microbial degradation of the dinoflagellate \textitScrippsiella trochoidea, Geochim. Cosmochim. Ac., 69(8), 2111–2117, 2005. Arnarson, T. S. and Keil, R. G.: Changes in organic matter-mineral interactions for marine sediments with varying oxygen exposure times, Geochim. Cosmochim. Ac., 71, 3545–3556, 2007. Armstrong, R. A., Peterson, M. L., Lee, C., and Wakeham, S. G.: Settling velocity spectra and the ballast ratio hypothesis, Deep Sea Res. Pt II, 56, 1470–1478, 2009. Arnosti, C., Ziervogel, K., Ocampo, L., and Ghobrial, S.: Enzyme activities in the water column and in shallow permeable sediments from the northeastern Gulf of Mexico, Estuar. Coast. Shelf S., 84, 202–208, 2009. Bahri, H., Dignac, M. F., Rumpel, C., Rasse, D. P., Chenu, C., and Mariotti, A.: Lignin turnover kinetics in an agricultural soil is monomer specific, Soil Biol. Biochem., 38(7), 1977–1988, 2006. Bastviken, D., Persson, L., Odham, G., and Tranvik, L.: Degradation of dissolved organic matter in oxic and anoxic lake water, Limnol. Oceanogr., 49, 109–116, 2004. Bauer, J. E., Williams, P. M., and Druffel, E. R. M.: $^14$C activity of dissolved organic carbon fractions in the north-central Pacific and Sargossa Sea, Nature, 357, 667–670, 1992. Bernstein, R. E., Byrne, R. H., Betzer, P. R., and Greco, A. M.: Morphologies and transformations of celestite in seawater: The role of acantharians in strontium and barium geochemistry, Geochim. Cosmochim. Ac., 56(8), 3273–3279, 1992. Bertram, M. A. and Cowen, J. P.: The form, composition and origin of marine barite, Eos, 75, 382, 1994. Bianchi, T. S., Wysocki, L. A., Stewart, M., Filley, T. R., and McKee, B. A.: Temporal variability in terrestrially-derived sources of particulate organic carbon in the lower Mississippi River and its upper tributaries, Geochim. Cosmochim. Ac., 71(18), 4425–3744, 2007. Bishop, J. K. B.: The barite-opal-organic carbon association in oceanic particulate matter, Nature, 332, 341–343, 1988. Blom, A. V.: Quelques remarques sur le mécanisme de séchage des peintures à l'huile, Peintures, Pigments, Vernis, 13, 156–162, 1936. Bockelmann, F.-D.: Selective preservation of organic-walled dinoflagellate cysts in Quaternary marine sediments: An oxygen effect and its application to paleoceanography, Ph.D., Bremen University, 1–130, 2007. Brassell, S. C., Eglinton, G., Marlowe I. T., Pflaumann U., and Sarnthein, M.: Molecular stratigraphy: a new tool for climatic assessment, Nature, 320, 129–133, 1986. Brunelle, B. G., Sigman, D. M., Cook, M. S., Keigwin, L. D., Haug, G. H., Plessen, B., Schettler, G., and Jaccard, S. L.: Evidence from diatom-bound nitrogen isotopes for subarctic Pacific stratification during the last ice age and a link to North Pacific denitrification changes, Paleoceanogr., 22, 1–17, 2007. Burdige, D. J.: Burial of terrestrial organic matter in marine sediments: A re-assessment, Glob. Biogeochem. Cy., 19(4), GB4011, doi:10.1029/2004GB002368, 2005. Cacho, I., Grimalt, J. O., Sierro, F. J., Shackleton, N. J., and Canals, M.: Evidence for enhanced Mediterranean thermohaline circulation during rapid climatic coolings, Earth Planet. Sci. Lett., 183(3–4), 417–429, 2000. Canfield, D. E.: Factors influencing organic carbon preservation in marine sediments, Chem. Geol., 114, 315–329, 1994. Canfield, D. E. and Thamdrup, B.: Towards a consistent classification scheme for geochemical environments, or, why we wish the term "suboxic" would go away, Geobiol, 7, 385–392, 2009. Chow, T. J. and Goldberg, E. D.: On the marine geochemistry of barium, Geochim. Cosmochim. Ac., 20(3–4), 192–198, 1960. Cooke, M. P., Talbot, H. M., and Farrimond, P.: Bacterial populations recorded in bacteriohopanepolyol distributions in soils from Northern England, Org. Geochem., 39, 1347–1358, 2008. Coppola, L., Gustafsson, O., Andersson, R., Eglinton, T. I., Uchida, M., and Dickens, A. F.: The importance of ultrafine particles as a control on the distribution of organic carbon in Washington Margin and Cascadia Basin sediments, Chem. Geol., 243(1–2), 142–156, 2007. Collier, R. and Edmond, J.: The trace element geochemistry of marine biogenic particulate matter, Progr. Oceanogr., 13(2), 113–199, 1984. Czimczik, C. I. and Masiello, C. A.: Controls on black carbon storage in soils, Glob. Biogeochem. Cy., 21, GB3005, doi:10.1029/2006GB002798, 2007. Dauwe, B., Middelburg, J. J., Herman, P. M. J., and Heip, C. H. R.: Linking diagenetic alteration of amini acids and bulk organic matter reactivity, Limnol. Oceanogr., 44(7), 1809–1814, 1999. de Lange, G. J., Thomson, J., Reitz, A., Slomp, C. P., Principato, M. S., Erba, E., and Corselli, C.: Synchronous basin-wide formation and redox-controlled preservation of a Mediterranean sapropel, Nat. Geosci., 1, 606–610, 2008. de Leeuw, J. W.: On the origin of sedimentary aliphatic macromolecules: A comment on recent publications by Gupta et al., Org. Geochem., 38(9), 1585–1587, 2007. de Leeuw, J. W., Versteegh, G. J. M., and van Bergen, P. F.: Biomacromolecules of plants and algae and their fossil analogues, Plant. Ecol., 189, 209–233, doi:10.1007/s11258-005-9027-x, 2006. De Vargas, C., Aubry, M.-P., Probert, I., and Young, J.: Origin and evolution of Coccolithophores: from coastal hunters to oceanic farmers, in: Evolution of Primary Producers in the Sea, edited by: Falkowski, P. G. and Knoll, A., Academic Press, London, 251–285, 2007. Dehairs, F., Chesselet R., and Jedwab, J.: Discrete suspended particles of barite and the barium cycle in the open ocean, Earth Planet. Sci. Lett., 49(2), 528–550, 1980. Dehairs, F., Stroobants, N., and Goeyens, L.: Barite formation in the southern-ocean water column, Mar. Chem., 35(1–4), 399–410, 1991. Deutsch, C., Sigman, D. M., Thunell, R. C., Meckler, A. N., and Haug, G. H.: Isotopic constraints on glacial/interglacial changes in the oceanic nitrogen budget, Glob. Biogeochem. Cy., 18, GB4012, doi:10.1029/2003GB002189, 2004. Dignac, M. F., Bahri, H., Rumpel, C., Rasse, D. P., Bardoux, G., Balesdent, J., Girardin, C., Chenu, C., and Mariotti, A.: Carbon-13 natural abundance as a tool to study the dynamics of lignin monomers in soil: an appraisal at the Closeaux experimental field (France), Geoderma, 128(1–2), 3–17, 2005. Dittmar, T. and Koch, B. P.: Thermogenic organic matter dissolved in the abyssal ocean, Mar. Chem., 102(3–4), 208–217, 2006. Dorgan, K. M., Jumars, P. A., Johnson, B., Boudreau, B. P., and Landis, E.: Burrowing mechanics: Burrow extension by crack propagation, Nature, 433, 475, 2005. Dymond, J., Suess, E., and Lyle, M.: Barium in deep-sea sediment: a geochemical indicator of paleoproductivity, Paleoceanogr., 7, 163–181, 1992. Eglinton, T. I., Conte, M. H., Eglinton, G., and Hayes, J. M.: Proceedings of a workshop on alkenone-based paleoceanographic indicators, Geochem. Geophys. Geosyst., 2, 2000GC000122, doi:10.1029/2000GC000122, 2001. Farrell, J. W., Pedersen, T. F., Calvert, S. E., and Nielsen, B.: Glacial-interglacial changes in nutrient utilization in the equatorial Pacific Ocean, Nature, 377, 514–517, 1995. Francois, R., Honjo, S., Manganini, S. J., and Ravizza, G. E.: Biogenic barium fluxes to the deep-sea: implications for paleoproductivity reconstruction, Glob. Biogeochem. Cy., 9(2), 289–301, 1995. Froelich, P. N., Klinkhammer, G. P., Bender, M. L., Luedtke, N. A., Heath, G. R., Cullen, D., Dauphin, P., Hammond, D., Hartman, B., and Maynard, V.: Early oxidation of organic matter in pelagic sediments of the eastern equatorial Atlantic: suboxic diagenesis, Geochim. Cosmochim. Ac., 43, 1075–1090, 1979. Ganeshram, R. S., François, R., Commeau, J., and Brown-Leger, S. L.: An experimental investigation of barite formation in seawater, Geochim. Cosmochim. Ac, 67(14), 2599–2605, 2003. Ganeshram, R. S., Pedersen, T. F., Calvert, S. E., and François, R.: Reduced nitrogen fixation in the glacial ocean inferred from changes in marine nitrogen and phosphorus inventories, Nature, 415(6868), 156–159, 2002. Ganeshram, R. S., Pedersen, T. F., Calvert, S. E., McNeill, G. W., and Fontugne, M. R.: Glacial-interglacial variability in denitrification in the world's oceans: causes and consequences, Paleoceanogr., 15(4), 361–376, 2000. Gaye-Haake, B., Lahajnar, N., Emeis, K.-C., Unger, D., Rixen, T., Suthhof, A., Ramaswamy, V., Schulz, H., Paropkari, A. L., Guptha, M. V. S., and Ittekkot, V.: Stable nitrogen isotopic ratios of sinking particles and sediments from the northern Indian Ocean, Mar. Chem., 96(3–4), 243–255, 2005. Gingele, F. and Dahmke, A.: Discrete barite particles and barium as tracers of paleoproductivety in South Atlantic sediments, Paleoceanogr., 9(1), 151–168, 1994. Gingele, F. X., Zabel, M., Kasten, S., Bonn, W. J., and Nürnberg, C. C.: Biogenic barium as proxy for paleoproductivity: methods and limitations of application, in: Use of Proxies in Oceanography, edited by: Fischer, G. and Wefer, G., Springer, Berlin, 365–392, 1999. Gleixner, G., Poirier, N., Bol, R., and Balesdent, J.: Molecular dynamics of organic matter in a cultivated soil, Org. Geochem., 33(3), 357–366, 2002. Glud, R. N.: Oxygen dynamics of marine sediments, Mar. Biol. Res., 4(4), 243–289, 2008. Godhe, A., Norén, F., Kulenstierna, M., Ekberg, C., and Karlson, B.: Relationship between planktonic dinoflagellate abundance, cysts recovered in sediment traps and environmental factors in the Gullmar Fjord, Sweden, J. Plankton Res., 23(9), 923–938, 2001. Goldberg, E. D. and Arrhenius, G. O. S.: Chemistry of Pacific pelagic sediments, Geochim. Cosmochim. Ac., 13(2–3), 199–212, 1958. Gong, C. and Hollander D. J.: Evidence for differential degradation of alkenones under contrasting bottom water oxygen conditions: Implication for paleotemperature reconstruction, Geochim. Cosmochim. Ac., 63, 405–411, 1999. Goñi, M. A., Yunker, M. B., Macdonald, R. W., and Eglinton, T. I.: The supply and preservation of ancient and modern components of organic carbon in the Canadian Beaufort Shelf of the Arctic Ocean, Mar. Chem., 93(1), 53–73, 2005. Gooday, A. J. and Nott, J. A.: Intracellular barite cystals in two Xenophyophores, \textitAschemonella ramuliformis and \textitGalatheammina sp. (protozoa: rhizopoda) with comments on the taxonomy of \textitA. ramuliformis., J. Mar. Biol. Ass. UK, 62(3), 595–605, 1982. Gough, M. A., Fauzi, R., Mantoura, C., and Preston, M.: Terrestrial plant biopolymers in marine sediments. Geochim. Cosmochim. Ac., 57, 945–964, 1993. Guerra-Garcia, J. M. and García-Gómez, J. C.: Oxygen labels versus chemical pollutants: do they have similar influence on macrofaunal assemblages? A case study in a harbour with two opposing entrances, Environ. Pollut., 135, 281–291, 2005. Gupta, N. S., Michels, R., Briggs, D. E. G., Collinson, M. E., Evershed, R. P., and Pancost, R. D.: Experimental evidence for the formation of geomacromolecules from plant leaf lipids, Org. Geochem., 38(1), 28–36, 2007. Haider, K. K.: Problems related to the humification processes in soils of the temperate climate, in: Soil Biochemistry, edited by: Bollag, J.-M., Marcel Dekker, New York, 55–94, 1992. Hanford, M. J. and Peeples, T. L.: Archaeal tetraether lipids, Appl. Biochem. Biotechnol., 97(1), 45–62, 2002. Hartnett, H. E., Keil, R. G., Hedges, J. I., and Devol, A. H.: Influence of oxygen exposure time on organic carbon preservation in continental margin sediments, Nature, 391, 572–574, 1998. Harvey, G. R., Boran D. A., Chesal, L. A., and Tokar, J. M.: The structure of marine fulvic and humic acid, Mar. Chem., 12, 119–132, 1983. Haug, G. H., Pedersen, T. F., Sigman, D. M., Calvert, S. E., and Nielsen, B.: Glacial/interglacial variations in production and nitrogen fixation in the Cariaco Basin during the last 580 kyr, Paleoceanogr., 13(5), 427–432, 1998. Hedges, J. I., Cowie, G. L., Richey, J. E., Quay, P. D., Brenner, R., Strom, M., and Forsberg, B.: Origin and processing of organic matter in the Amazon River as indicated by carbohydrates and amino acids, Limnol. Oceanogr., 39(4), 743–761, 1994. Hedges, J. I., Eglinton, G., Hatcher, P. G., Kirchman, D. L., Arnosti, C., Derenne, S., Evershed, R. P., Kögel-Knabner, I., de Leeuw, J. W., Littke, R., Michaelis, W., and Rullkötter, J.: The molecularly-uncharacterized component of nonliving organic matter in natural environments, Org. Geochem., 31, 945–958, 2000. Hedges, J. I., Hu, F. S., Devol, A. H., Hartnett, H. E., Tsamakis, E., and Keil, R. G.: Sedimentary organic matter preservation: a test for selective degradation under oxic conditions, Am. J. Sci., 229, 529–555, 1999. Hedges, J. I. and Keil, R. G.: Sedimentary organic matter preservation: an assessment and speculative synthesis, Mar. Chem., 49, 81–115, 1995. Hedges, J. I. and Keil, R. G.: Organic geochemical perspectives on estuarine processes: sorption reactions and consequences, Mar. Chem., 65, 55–65, 1999. Hedges, J. I. and Mann, D. C.: The characterization of plant tissues by their lignin oxidation products, Geochim. Cosmochim. Ac., 43, 1803–1807, 1979. Hedges, J. I. and Oades, J. M.: Comparative organic geochemistries of soils and marine sediments, Org. Geochem., 27, 319–361, 1997. Hedges, J. I. and Prahl, F. G.: Early diagenesis: consequences for applications of molecular biomarkers, in: Organic Geochemistry, Principles and Applications, edited by: Engel, M. H., Macko, S. A., and Jones, D. S., Plenum Press, New York, 237–253, 1993. Heim, A. and Schmidt, M. W. I.: Lignin is preserved in the fine silt fraction of an arable Luvisol, Org. Geochem., 38(12), 2001–2011, 2007. Hemsley, A. R., Barrie, P. J., and Chaloner, W. G.: Studies of fossil and modern spore and pollen wall biomacromolecules using $^13$C solid state NMR, NERC Spec. Publ., 94(1), 15–19, 1994. Herbert, T. D.: Alkenone paleotemperature determinations, in: The Oceans and marine geochemistry, edited by: Elderfield, H., Elsevier, Amsterdam, 391–432, 2003. Herman, J. P., Middelburg, J. J., van de Koppel, J., and Heip, C. H. R.: Ecology of estuarine macrobenthos, Adv. Ecol. Res., 29, 195–240, 1999. Hertkorn N., Benner, R., Frommberger, M., Schmitt-Kopplin, P., Witt, M., Kaiser, K., Kettrup, A., and Hedges, J. I.: Characterization of a major refractory component of marine dissolved organic matter, Geochim. Cosmochim. Ac., 70(12), 2990–3010, 2006. Hilton, R. G., Galy, A., Hovius, N., Chen, M.-C., Horng, M.-J., and Chen, H.: Tropical-cyclone-driven erosion of the terrestrial biosphere from mountains, Nat. Geosci., 1, 759–762, 2008. Higgs, N. C., Thomson, J., Wilson, T. R. S., and Croudace, I. W.: Modification and complete removal of eastern Mediterranean sapropels by postdepositional oxidation, Geology, 22, 423–426, 1994. Hillenbrand, K.-D., Grobe, H., Diekmann, B., Kuhn, G., and Fütterer, D. K.: Distribution of clay minerals and proxies for productivity in surface sediments of the Bellingshausen and Amundsen seas (West Antarctica) – Relation to modern environmental conditions, Mar. Geol., 193(3–4), 253–271, 2003. Hockaday, W. C., Grannas, A. M., Kim, S., and Hatcher, P. G.: Direct molecular evidence for the degradation and mobility of black carbon in soils from ultrahigh-resolution mass spectral analysis of dissolved organic matter from a fire-impacted forest soil, Org. Geochem., 37(4), 501–510, 2006. Hoefs, M. J. L., Rijpstra, W. I. C., and Sinninghe Damsté, J. S.: The influence of oxic degradation on the sedimentary biomarker record I: Evidence from Madeira Abyssal Plain turbidites, Geochim. Cosmochim. Ac., 66, 2719–2735, 2002. Hoefs, M. J. L., Versteegh, G. J. M., Rijpstra, W. I. C., de Leeuw, J. W., and Sinninghe Damsté, J. S.: Postdepositional oxic degradation of alkenones: implications for the measurement of palaeo sea surface temperatures, Paleoceanogr., 13(1), 42–49, 1998. Holmes, E., Lavik, G., Fischer, G., and Wefer, G.: Nitrogen isotopes in sinking particles and surface sediments, in: The South Atlantic in the Late Quaternary, edited by: Wefer, G., Mulitza, S., and Rathmeyer, V., Springer, Berlin, 143–165, 2003. Hopkins, J. A. and McCarthy, F. M. G.: Post-depositional palynomorph degradation in Quaternary shelf sediments: a laboratory experiment studying the effects of progressive oxidation, Palynol., 26, 167–184, 2002. Hopmans, E. C., Weijers, J. W. H., Schefuss, E., Herfort, L., Sinninghe Damsté, J. S., and Schouten, S.: A novel proxy for terrestrial organic matter in sediments based on branched and isoprenoid tetraether lipids, Earth Planet. Sci. Lett., 224(1–2), 107–116, 2004. Hughey, C. A., Minardi, C. S., Galasso-Roth, S. A., Paspalof, G. B., Mapolelo, M. M., Rodgers, R. P., Marshall, A. G., and Ruderman, D. L.: Naphthenic acids as indicators of crude oil biodegradation in soil, based on semi-quantitative electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry, Rapid Commun. Mass Sp., 22, 3968–3976, 2008. Huang, Y., Li, B., Bryant, C., Bol, R., and Eglinton, T. I.: Radiocarbon dating of aliphatic hydrocarbons: A new approach for dating passive-fraction carbon in soil horizons, Soil Sci. Soc. Am. J., 63, 1181–1187, 1999. Huguet, C., de Lange, G. J., Gustafsson, O., Middelburg, J. J., Sinninghe Damsté, J. S., and Schouten, S.: Selective preservation of soil organic matter in oxidized marine sediments (Madeira Abyssal Plain), Geochim. Cosmochim. Ac., 72(24), 6061–6068, 2008. Huguet, C., de Lange, G. J., Kim, J.-H., Sinninghe Damsté, J. S., and Schouten, S.: Selective preservation of soil-derivedglycerol diakyl glycerol tetraether lipids in oxidized marine sediments, in: TEX$_86$ Paleothermometry: Proxy validation and application in marine sediments, edited by: Huguet, C., Utrecht University, Utrecht, 87–104, 2007. Huguet, C., Kim, J.-H., de Lange, G. J., Sinninghe Damsté, J. S., and Schouten, S.: Effects of long-term oxic degradation on the U$^K´_37$, TEX$_86$ and BIT organic proxies, Org. Geochem., 40, 1188–1194, 2009. Ishikawa A. and Taniguchi A.: Contribution of benthic cysts to the population dynamics of \textitScrippsiella spp. (Dinophyceae) in Onagawa Bay, northeast Japan, Mar. Ecol. Progr. Ser., 140, 169-178, 1996 Jenkyns, H. C., Gröcke, D. R., and Hesselbo, S. P.: Nitrogen isotope evidence for water mass denitrification during the Early Toarcian (Jurassic) oceanic anoxic event, Paleoceanogr., 16(6), 593–603, 2001. Jorge, R. M. F. and Livingston, A. G.: A novel method for characterisation of microbial growth kinetics on volatile organic compounds, Appl. Microbiol., 52, 174–178, 1999. Jung, M., Ilmberger, J., Mangini, A., and Emeis, K.-C.: Why some Mediterranean sapropels survived burn-down (and others did not), Mar. Geol., 141, 51–60, 1997. Kasten, S., Haese, R. R., Zabel, M., Rühlemann, C., and Schulz, H. D.: Barium peaks at glacial terminations in sediments of the equatorial Atlantic Ocean – relicts of deglacial productivity pulses?, Chem. Geol., 175, 635–651, 2001. Kasten, S., Zabel, M., Heuer, V., and Hensen, C.: Processes and signals of non-steady state diagenesis in deep-sea sediments, in: The South Atlantic in the Late Quaternary, edited by: Wefer, G., Mulitza, S., and Rathmeyer, V., Springer, Berlin, 431–459, 2003. Keil, R. G., Tsamakis, E., Giddings, J. C., and Hedges, J. I.: Biochemical distributions (amino acids, neutral sugars, and lignin phenols) among size-classes of modern marine sediments from Washington coast, Geochim. Cosmochim. Ac., 62, 1347–1364, 1998. Khanna, R., Witt, M., Anwer, K., Agarwal, S. P., and Koch, B. P.: Spectroscopic characterization of Fulvic Acids extracted from the rock exudate Shilajit, Org. Geochem. 39, 1719–1724, 2008. Kiem, R. and Kögel-Knabner, I.: Contribution of lignin and polysaccharides to the refractory carbon pool in C-depleted arable soils, Soil Biol. Biochem., 35(1), 101–118, 2003. Kim, J.-H., Huguet, C., Zonneveld, K. A. F., Versteegh, G. J. M., Sinninghe Damsté, J. S., and Schouten, S.: Stability of the TEX$_86$ and U$^K'_37$ temperature proxies upon a one year field incubation experiment., Org. Geochem., 73, 2888–2898, 2009. Kim, S. W., Kaplan, L. A., Benner, R., and Hatcher, P. G.: Hydrogen-deficient molecules in natural riverine water samples – evidence for the existence of black carbon in DOM, Mar. Chem., 92(1–4), 225–234, 2004. Knicker, H. and Hatcher, P. G.: Survival of protein in an organic-rich sediment; possible protection by encapsulation in organic matter, Naturwissenschaften, 84(6), 231–234, 1997. Knicker, H. and Hatcher, P. G.: Sequestration of organic nitrogen in the sapropel from Mangrove Lake, Bermuda, Org. Geochem., 32(5), 733–744, 2001. Koch, B. P. and Dittmar, T.: From mass to structure: an aromaticity index for high-resolution mass data of natural organic matter, Rapid Commun. Mass. Sp., 20(5), 926–932, 2006. Koch, B. P., Ludwichowski, K. U., Kattner, G., Dittmar, T., and Witt, M.: Advanced characterization of marine dissolved organic matter by combining reversed-phase liquid chromatography and FT-ICR-MS, Mar. Chem., 111, 233–241, 2008. Koch, B. P., Witt M., Engbrodt R., Dittmar T., and Kattner, G.: Molecular formulae of marine and terrigenous dissolved organic matter detected by electrospray ionization fourier transform ion cyclotron resonance mass spectrometry, Geochim. Cosmochim. Ac., 69(13), 3299–3308, 2005. Koch, B. P., Witt M., Kattner, G., and Dittmar, T.: Fundamentals of molecular formula assignment to ultrahigh resolution mass data of natural organic matter, Anal. Chem., 79, 1758–1763, 2007. Kodrans-Nsiah, M., Zonneveld, K. A. F., and de Lange, G. J.: Species-selective aerobic degradation of dinoflagellate cysts – results of a natural exposure experiment, Rev. Palaeobot. Palyno., 152, 32–39, 2008. Kokinos, J. P., Eglinton, T. I., Goñi, M. A., Boon, J. J., Martoglio, P. A., and Anderson, D. M.: Characterisation of a highly resistant biomacromolecular material in the cell wall of a marine dinoflagellate resting cyst, Org. Geochem., 28(5), 265–288, 1998. Kramer, R. W., Kujawinski, E. B., and Hatcher, P. G.: Identification of black carbon derived structures in a volcanic ash soil humic acid by Fourier transform ion cyclotron resonance mass spectrometry, Env. Sci. Technol., 38, 3387–3395, 2004. Kremp, A. and Heiskanen, A.-S.: Sexuality and cyst formation of the spring-bloom dinoflagellate \textitScrippsiella hangoei in the coastal northern Baltic Sea, Mar. Biol., 134, 771–777, 1999. Kujawinski, E. B., Del Vecchio, R., Blough, N. V., Klein, G. C., and Marshall, A. G.: Probing molecular-level transformations of dissolved organic matter: insights on photochemical degradation and protozoan modification of DOM from electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry., Mar. Chem., 92(1–4), 23–37, 2004. Kujawinski, E. B., Freitas, M. A., Zang, X., Hatcher, P. G., Green-Church, K. B., and Jones, R. B.: The application of electrospray ionization mass spectrometry (ESI MS) to the structural characterization of natural organic matter, Org. Geochem., 33(3), 171–180, 2002. Laws, E. A., Popp, B. N., Bidigare, R. R., Riebesell, U., Burkhardt, S., and Wakeham, S. G.: Controls on the molecular distribution and carbon isotopic composition of alkenones in certain haptophyte algae, Geochem. Geophys. Geosys., 2, 2000GC000057, doi:10.1029/2000GC000057, 2001. Lehmann, M. F., Bernasconi, S. M., Barbieri, A., and McKenzie, J. A.: Preservation of organic matter and alteration of its carbon and nitrogen isotope composition during simulated and in situ early sedimentary diagenesis, Geochim. Cosmochim. Ac., 66(20), 3573–3584, 2002. Libes, S. M. and Deuser, W. G.: The isotope geochemistry of particulate nitrogen in the Peru upwelling area and the Gulf of Maine, Deep-Sea Res., 35(4), 517–533, 1988. Marret, F.: Les effets de l'acétolyse sur les assemblages des kystes de dinoflagellés, Palynosci., 2, 267–272, 1993. Marret, F. and Zonneveld, K. A. F.: Atlas of modern organic-walled dinoflagellate cyst distribution, Rev. Palaeobot. Palyno., 125(1), 1–200, 2003. Marschner, B., Brodowski, S., Dreves, A., Gleixner, G., Gude, A., Grootes, P. M., Hamer, U., Heim, A., Jandl, G., Ji, R., Kaiser, K., Kalbitz, K., Kramer, C., Leinweber, P., Rethemeyer, J., Schaeffer, A., Schmidt, M. W. I., Schwark, L., and Wiesenberg, G. L. B.: How relevant is recalcitrance for the stabilization of organic matter in soils?, J. Plant. Nutr. Soil Sci., 171(1), 91–110, 2008. Marshall, A. G., Hendrickson, C. L., and Jackson, G. S.: Fourier transform ion cyclotron resonance mass spectrometry: A primer, Mass Spectr. Rev., 17(1), 1–35, 1998. Martrat, B., Grimalt, J. O., Shackleton, N. J., de Abreu, L., Hutterli, M. A., and Stocker, T. F.: Four climate cycles of recurring deep and surface water destabilisations on the Iberian Margin, Science, 317, 502–507, 2007. Matthewson, A. P., Shimmield, G. B., Kroon, D., and Fallick, A. E.: A 300 kyr high-resolution aridity record of the North African continent, Paleoceanogr., 10(3), 667–692, 1995. McKenna, A. M., Purcell, J. M., Rodgers, R. P., and Marshall, A. G.: Identification of vanadyl porphyrins in a heavy crude oil and raw asphaltene by atmospheric pressure photoionization fourier transform Ion cyclotron resonance (FT-ICR) mass spectrometry, Energy Fuel., 23(4), 2122–2128, 2009. Meier, K. J. S., Zonneveld, K. A. F., Kasten, S., and Willems, H.: Different nutrient sources forcing increased productivity during eastern Mediterranean S1 sapropel formation as reflected by calcareous dinoflagellate cysts., Paleoceanogr., 19, PA1012, doi:10.1029/2003PA000895, 2004. Meysman, F. J. R., Middelburg, J. J., and Heip, C. H. R.: Bioturbation: A fresh look at Darwin's last idea, Trends Ecol. Evol., 21(12), 688–695, 2006. Middelburg, J. J. and Meysman, F. J. R.: Burial at sea, Science, 316, 1294–1295, 2007. Möbius, J., Gaye, B., Lahajnar, N., Bahlmann, E., and Emeis, K.-C.: Influences on sedimentary $\delta ^15$N in the Arabian Sea over the last 130 kyr, submitted to Geochim Gosmochim Ac., 2010. Mollenhauer, G. and Eglinton, T. I.: Diagenetic and sedimentological controls on the composition of organic matter preserved in California Borderland Basin sediments, Limnol. Oceanogr., 52(2), 558–576, 2007. Mollenhauer, G., Inthorn, M., Vogt, T., Zabel, M., Sinninghe Damsté, J. S., and Eglinton, T. I.: Aging of marine organic matter during cross-shelf lateral transport in the Benguela upwelling system revealed by compound-specific radiocarbon dating, Geochem. Geophys. Geosys., 8(9), Q09004, doi:10.1029/2007GC001603, 2007. Monnin, C., Jeandel, C., Cattaldo, T., and Dehairs, F.: The marine barite saturation state of the world's oceans, Mar. Chem., 65(3–4), 253–261, 1999. Montresor, M., Zingone, A., and Sarno, D.: Dinoflagellate cyst production at a coastal Mediterranean site, J. Plankton Res., 20(12), 2291–2312, 1998. Moodley, L., Middelburg, J. J., Soetaert, K., Boschker, H. T. S., Herman, P. M. J., and Heip, C. H. R.: Similar rapid response to phytodetritus deposition in shallow and deep-sea sediments, J. Mar. Res., 63(2), 457–469, 2005. Moore, W. S., Sarmiento, J. L., and Key, R. M.: Submarine groundwater discharge revealed by $^228$Ra distribution in the upper Atlantic Ocean, Nat. Geosci., 1(5), 309–311, doi:10.1038/ngeo183, 2008. Moreno, A., Nave, S., Kuhlmann, H., Canals, M., Targarona, J., Freudenthal, T., and Abrantes, F.: Productivity response in the North Canary Basin to climate changes during the last 250000 yr: a multi-proxy approach, Earth Planet. Sci. Lett., 196(3–4), 147–159, 2002. Mudie, P. J. and McCarthy, F. M. G.: Marine palynology: potentials for onshore-offshore correlation of Pleistocene-Holocene records, Trans. Royal Soc. S. Afr., 61(2), 139–157, 2006. Nürnberg, C. C., Bohrmann, G., Schlüter, M., and Frank, M.: Barium accumulation in the Atlantic sector of the Southern Ocean: Results from 190000-year records, Paleoceanogr., 12(4), 594–603, 1997. Ohkouchi, N., Eglinton, T. I., Keigwin, L. D., and Hayes, J. M.: Spatial and temporal offsets between proxy records in a sediment drift. Science, 298, 1224–1227, 2002. Opsahl, S. and Brenner, R.: Distribution and cycling of terrigenous dissolved organic matter in the ocean, Nature, 386, 480–482, 1997. Otto, A. and Simpson, M. J.: Evaluation of CuO oxidation parameters for determining the source and stage of lignin degradation in soil, Biogeochem., 80, 121–142, 2006. Parkes, R. J., Cragg, B. A., Getliff, J. M., Harvey, S. M., Fry, S. E., Lewis, C. A., and Rowland, S. J.: A quantitative study of microbial decomposition of biopolymers in Recent sediments from the Peru Margin, Mar. Geol., 113, 55–66, 1993. Passier, H. F., Bosch, H.-J., Nijenhuis, I. A., Lourens, L. J., Böttcher, M. E., Leenders, A., Sinninghe Damsté, J. S., de Lange, G. J., and de Leeuw, J. W.: Sulphidic Mediterranean surface waters during Pliocene sapropel formation, Nature, 397, 146–149, 1999. Pearson, A. and Eglinton, T. I.: The origin of $n$-alkanes in Santa Monica Basin surface sediment: a model based on compound-specific $\Delta ^14$C and $\delta ^13$C data, Org. Geochem., 31(11), 1103–1116, 2000. Pfeifer, K., Kasten, S., Hensen, C., and Schulz, H. D.: Reconstruction of primary productivity from the barium contents in surface sediments of the South Atlantic Ocean, Mar. Geol., 177(1/2), 13–24, 2001. Pfiester, L. A. and Anderson, D. M.: Dinoflagellate life-cycles and their environmental control, in: The biology of dinoflagellates, edited by: Taylor, F. J. R., Blackwell Scientific Publishers, Oxford, 611–648, 1987. Prahl, F. G.: Prospective use of molecular paleontology to test for iron limitation on marine primary productivity, Mar. Chem., 39(1–3), 167–185, 1992. Prahl, F. G., Collier, R. B., Dymond, J., Lyle, M., and Sparrow, M. A.: A biomarker perspective on prymnesiophyte productivity in the northeast Pacific Ocean, Deep-Sea Res. Pt I, 40(10), 2061–2076, 1993. Prahl, F. G., Cowie, G. L., de Lange, G. J., and Sparrow, M. A.: Selective organic matter preservation in "burn-down" turbidites on the Madeira Abyssal Plain, Paleoceanogr., 18(2), 1052, doi:2002PA000853, 2003. Prahl, F. G., de Lange, G. J., Lyle, M., and Sparrow, M. A.: Post-depositional stability of long-chain alkenones under contrasting redox conditions, Nature, 341, 434–437, 1989. Prahl, F. G., Dymond, J., and Sparrow, M. A.: Annual biomarker record for export production in the central Arabian Sea, Deep-Sea Res. Pt II, 47(7–8), 1581–1604, 2000. Prahl, F. G., Mix, A. C., and Sparrow, M. A.: Alkenone paleothermometry: Biological lessons from marine sediment records off western South America, Geochim. Cosmochim. Ac., 70(1), 101–117, 2006. Prahl, F. G. and Muehlhausen, L. A.: Lipid biomarkers as geochemical tools for paleoceanographic study, in: Productivity of the Ocean: Present and Past, edited by: Berger, W. H., Smetacek, V. S., and Wefer, G., Wiley, Chichester, 271–289, 1989. Qian, K., Mennito, A. S., Edwards, K. E., and Ferrughelli, D. T.: Observation of vanadyl porphyrins and sulfur-containing vanadyl porphyrins in a petroleum asphaltene by at- mospheric pressure photonionization Fourier transform ion cyclotron resonance mass spectrometry, Rapid Commun. Mass. Sp., 22, 2153–2160, 2008. Reemtsma, T., These, A., Venkatachari, P., Xia, X. Y., Hopke ,P. K., Springer, A., and Linscheid, M.: Identification of fulvic acids and sulfated and nitrated analogues in atmospheric aerosol by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry, Anal. Chem., 78(24), 8299–8304, 2006. Reitz, A., Pfeifer, K., de Lange, G. J., and Klump, J.: Biogenic barium and the detrital Ba/Al ratio: a comparison of their direct and indirect determination, Mar. Geol., 204(3–4), 289–300, 2004. Riedinger, N., Kasten, S., Gröger, J., Franke, C., and Pfeifer, K.: Active and buried authigenic barite fronts in sediments from the eastern Cape Basin. Earth Planet. Sci. Lett., 241 (3–4), 876–888, 2006. Rethemeyer, J., Kramer, C., Gleixner, G., Wiesenberg, G. L. B., Schwark, L., Andersen, N., Nadeau, M. J., and Grootes, P. M.: Complexity of soil organic matter: AMS $^14$C analysis of soil lipid fractions and individual compounds, Radiocarb., 46(1), 465–473, 2004. Rodgers, R. P., Hendrickson, C. L., Emmett, M. R., Marshall, A. G., Greaney, M., and Qian, K. N.: Molecular characterization of petroporphyrins in crude oil by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Can. J. Chem., 79, 546–551, 2001. Rontani, J.-F., Harji, R., Guasco, F., Prahl, F. G., Volkman, J. K., Bhosle, N. B., and Bonin, P.: Degradation of alkenones by aerobic heterotrophic bacteria: Selective or not?, Org. Geochem., 39, 34–51, 2008. Rontani, J.-F. and Wakeham, S. G.: Alteration of alkenone unsaturation ratio with depth in the Black Sea: Potential roles of stereomutation and aerobic biodegradation, Org. Geochem., 39(9), 1259–1268, 2008. Ross, O. N. and Sharples, J.: Swimming for survival: a role of phytoplankton motility in a stratified turbulent environment, J. Marine Syst., 70(3–4), 248–262, 2008. Sachs, J. P. and Repeta, D. J.: Oligotrophy and nitrogen fixation during Eastern Mediterranean sapropel events, Science, 286, 2485–2488, 1999. Schaub, T. M., Rodgers, R. P., Marshall, A. G., Qian, K., Green, L. A., and Olmstead, W. N.: Speciation of aromatic compounds in petroleum refinery streams by continuous flow field desorption ionization FT-ICR mass spectrometry, Energy Fuel., 19(4), 1566–1573, 2005. Schefuss, E., Schouten, S., and Schneider, R. R.: Climatic controls on central African hydrology during the past 20000 years, Nature, 437, 1003–1006, 2005. Schlesinger, W. H. and Melack, J. M.: Transport of organic carbon in the worlds rivers, Tellus, 33(2), 172–178, 1981. Schmidt, F., Elvert, M., Koch, B. P., Witt, M., and Hinrichs, K.-U.: Molecular characterization of dissolved organic matter in pore water of continental shelf sediments, Geochim. Cosmochim. Ac., 73(11), 3337–3358, 2009. Schneider, R. R., Price, B., Müller, P. J., Kroon, D., and Alexander, I.: Monsoon related variations in Zaire (Congo) sediment load and influence of fluvial silicate supply on marine productivity in the east equatorial Atlantic during the last 200000 years, Paleoceanogr., 12(3), 463–481, 1997. Schouten, S., Hopmans, E. C., and Sinninghe Damsté, J. S.: The effect of maturity and depositional redox conditions on archaeal tetraether lipid palaeothermometry, Org. Geochem., 35, 567–571, 2004. Schulte, S., Rostek, F., Bard, E., Rullkötter, J., and Marchal, O.: Variations of oxygen-minimum and primary productivity recorded in sediments of the Arabian Sea, Earth Planet. Sci. Lett., 173(3), 205–221, 1999. Schwarz, B., Mangini, A., and Segl, M.: Geochemistry of a piston core from Ontong Java plateau (western equatorial Pacific): Evidence for sediment redistribution and changes in paleoproductivity, Geol. Rundschau, 85(3), 536–545, 1996. Simon, A., Poulicek, M., Velimirov, B., and MacKenzie, F. T.: Comparison of anaerobic and aerobic biodegradation of mineralized skeletal structures in marine and estuarine conditions, Biogeochem., 25, 167–195, 1994. Sinninghe Damsté, J. S. and de Leeuw, J. W.: Analysis, structure and geochemical significance of organically-bound sulphur in the geosphere: State of the art and future research, Org. Geochem., 16, 1077–1101, 1990. Sinninghe Damsté, J. S. and Schouten, S.: Is there evidence for a substantial contribution of prokaryotic biomass to organic carbon in Phanerozoic carbonaceous sediments? Org. Geochem., 26, 517–530, 1997. Sinninghe Damsté, J. S., Kuypers, M. M. M., Schouten, S., Schulte, S., and Rullkötter, J.: The lycopane/C$_31 n$-alkane ratio as a proxy to assess palaeoxicity during sediment deposition, Earth Planet. Sci. Lett., 209(1–2), 215–226, 2003. Sinninghe Damsté, J. S., Rijpstra, W. I. C., and Reichart, G. J.: The influence of oxic degradation on the sedimentary biomarker record II, Evidence from Arabian Sea Sediments, Geochim. Cosmochim. Ac., 66, 2737–2754, 2002. Sleighter, R. L. and Hatcher, P. G.: Molecular characterization of dissolved organic matter (DOM) along a river to ocean transect of the lower Chesapeake Bay by ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry, Mar. Chem., 110(3–4), 140–152, 2008. Smittenberg, R. H., Eglinton, T. I., Schouten, S., and Sinninghe Damsté, J. S.: Ongoing buildup of refractory organic carbon in boreal soils during the Holocene, Science, 314(5803), 1283–1286, 2006. Sollins, P., Homann, P., and Caldwell, B. A.: Stabilization and destabilization of soil organic matter: mechanisms and controls, Geoderma, 74(1–2), 65–105, 1996. Stenson, A. C., Marshall, A. G., and Cooper, W. T.: Exact masses and chemical formulas of individual Suwannee River fulvic acids from ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectra, Anal. Chem., 75(8), 1275–1284, 2003. Struck U., Emeis, K.-C., Voss, M., Christiansen, C., and Kunzendorf, H.: Records of southern and central Baltic Sea eutrophication in $\delta ^13$C and $\delta ^15$N of sedimentary organic matter, Mar. Geol., 164(3–4), 157–171, 2000. Suess, E.: Particulate organic carbon flux in the oceans – surface productivity and oxygen utilization, Nature, 288, 260–263, 1980. Sun M.-Y. and Wakeham, S. G.: Molecular evidence for degradation and preservation of organic matter in the anoxic Black Sea Basin, Geochim. Cosmochim. Ac., 58, 3395–3406, 1994. Susek E., Zonneveld, K. A. F., Fischer, G., Versteegh, G. J. M., and Willems, H.: Organic-walled dinoflagellate cyst production related to variations in upwelling intensity and lithogenic influx in the Cape Blanc region (off NW Africa), Phycol. Res., 53(2), 97–112, 2005. Teece, M. A., Getliff, J. M., Leftley, J. W., Parkes, R. J., and Maxwell, J. R.: Microbial degradation of the marine prymnesiophyte \textitEmiliania huxleyi under oxic and anoxic conditions as a model for early diagenesis: long chain alkadienes, alkenones and alkyl alkenoates, Org. Geochem., 29, 863–880, 1998. Tendal, O. S.: A monograph of the Xenophyophoria (Rhizopoda, Protozoa), Galathea Report, 12, 1–103, 1972. Thomson, J., Higgs, N. C., Wilson, T. R. S., Croudace, I. W., de Lange, G. J., and van Santvoort, P. J. M.: Redistribution and geochemical behaviour of redox-sensitive elements around S1, the most recent eastern Mediterranean sapropel, Geochim. Cosmochim. Ac., 59(17), 3487–3501, 1995. Thomson, J., Mercone, D., de Lange, G. J., and van Santvoort, P. J. M.: Review of recent advances in the interpretation of eastern Mediterranean sapropel S1 from geological evidence, Mar. Geol., 153, 77–89, 1999. Torres, M. E., Brumsack, H. J., Bohrmann, G., and Emeis, K. C.: Barite fronts in continental margin sediments: a new look at barium remobilization in the zone of sulfate reduction and formation of heavy barites in diagenetic fronts, Chem. Geol., 127(1–3), 125–139, 1996. Trumbore, S. E. and Zheng, S. H.: Comparison of fractionation methods for soil organic matter 14C analysis, Radiocarb., 38(2), 219–229, 1996. van Dongen, B. E.: Natural sulfurization of carbohydrates in marine sediments: consequences for the chemical and carbon isotopic composition of sedimentary organic matter, Geol. Ultratrajectina, 224, 1–149, 2003. van Nugteren, P., Herman, P. M. J., Moodley, L., Middelburg, J. J., Vos, M., and Heip, C. H. R.: Spatial distribution of detrital resources determines the outcome of competition between bacteria and a facultative detrivorous worm, Limnol. Oceanogr., 54(4), 1413–1419, 2009. Van Os, B. H. H., Lourens, L. J., Hilgen, F. J., de Lange, G. J., and Beaufort L.: The formation of Pliocene sapropels and carbonate cycles in the Mediterranean – diagenesis, production and productivity, Paleoceanogr., 9(4), 601–617, 1994. van Santvoort, P. J. M., de Lange, G. J., Langereis, C. G., Dekkers, M. J., and Paterne, M.: Geochemical and paleomagnetic evidence for the occurrence of "missing" sapropels in eastern Mediterranean sediments, Paleoceanogr., 12(6), 773–786, 1997. van Santvoort, P. J. M., de Lange, G. J., Thomson, J., Cussen, H., Wilson, T. R. S., Krom, M. D., and Ströhle, K.: Active post-depositional oxidation of the most recent sapropel (S1) in sediments of the eastern Mediterranean Sea, Geochim. Cosmochim. Ac., 60, 4007–4024, 1996. Vandewiele, S., Cowie, G., Soetaert, K., and Middelburg, J. J.: Amino acid biogeochemistry and organic matter degradation state across the Pakistan margin oxygen minimum zone, Deep-Sea Res. Pt II, 56(6–7), 376–392, 2009. Versteegh, G. J. M. and Blokker, P.: Resistant macromolecules of extant and fossil microalgae, Phycol. Res., 52(4), 325–339, 2004. Versteegh, G. J. M., Blokker, P., Marshall, C. R., and Pross, J.: Macromolecular composition of the dinoflagellate cyst \textitThalassiphora pelagica (Oligocene, SW Germany), Org. Geochem., 38, 1643–1656, 2007. Versteegh, G. J. M., Blokker, P., Wood, G., Collinson, M. E., Sinninghe Damsté, J. S., and de Leeuw, J. W.: Oxidative polymerization of unsaturated fatty acids as a preservation pathway for microalgal organic matter, Org. Geochem., 35, 1129–1139, 2004. Versteegh, G. J. M., Riegman, R., de Leeuw, J. W., and Jansen, J. H. F.: U$^K'_37$ values for \textitIsochrysis galbana as a function of culture temperature, light intensity and nutrient concentrations, Org. Geochem., 32, 785–794, 2001. Versteegh, G. J. M. and Zonneveld, K. A. F.: Use of selective degradation to separate preservation from productivity, Geology, 30(7), 615–618, 2002. Villanueva, J., Grimalt, J. O., Labeyrie, L. D., Cortijo, E., Vidal, L., and Turon, J.-L.: Precessional forcing of productivity in the North Atlantic Ocean, Paleoceanogr., 13(6), 561–571, 1998. von Lützow, M., Kögel-Knabner, I., Ekschmitt, K., Heinz, F., Guggenberger, G., Matzner, E., and Marschner, B.: SOM fractionation methods: Relevance to functional pools and to stabilization mechanisms, Soil Biol. Biochem., 39(9), 2183–2207, 2007. Wada, E., Goldberg, E. D., Horibe, Y., and Saruhashi, K.: Nitrogen isotope fractionation and its significance in biogeochemical processes occurring in marine environments, in: Isotope Marine Chemistry, edited by: Goldberg, E. D., Horibe, Y., and Saruhashi, K., Uchida Rokakuho, Tokyo, 375–398, 1980. Wakeham, S. G. and Canuel, E. A.: Degradation and preservation of organic matter in marine sediments, in: Handbook of Environmental Chemistry, Hutzinger, O., Springer, Berlin, 295–321, 2006. Wakeham, S. G., Lee, C., Hedges, J. I., Hernes, P. J., and Peterson, M. L.: Molecular indicators of diagenetic status in marine organic matter, Geochim. Cosmochim. Ac., 61, 5363–5369, 1997. Wakeham, S. G., Peterson, M. L., Hedges, J. I., and Lee, C.: Lipid biomarker fluxes in the Arabian Sea, with a comparison to the equatorial Pacific Ocean, Deep-Sea Res. Pt II, 49(12), 2265–2301, 2002. Walinsky, S. E., Prahl, F. G., Mix, A. C., Finney, B. P., Jaeger, J. M., and Rosen, G. P.: Distribution and composition of organic matter in surface sediments of coastal Southeast Alaska. Cont. Shelf Res., 29, 1565–1579, 2009. Weijers, J. W. H., Schouten, S., Spaargaren, O. C., and Sinninghe Damsté, J. S.: Occurrence and distribution of tetraether membrane in soils: Implications for the use of the BIT index and the TEX$_86 $SST proxy, Org. Geochem., 37, 1680–1693, 2006. Weldeab, S., Emeis, K.-C., Hemleben, C., Schmiedl, G., and Schulz, H.: Spatial productivity during formation of Sapropels S5 and S6 in the Mediterranean Sea: evidence from Ba contents, Palaeogeogr. Palaeoclimatol. Palaeoecol., 191, 169–190, 2003a. Weldeab, S., Siebel, W., Wehausen, R., Emeis, K.-C., Schmiedl, G., and Hemleben, C.: Late Pleistocene sedimentation in the Western Mediterranean Sea: implications for productivity changes and climatic conditions in the catchment areas, Palaeogeogr. Palaeoclimatol. Palaeoecol., 190, 121–137, 2003b. Wiesenberg, G. L. B., Schwartzbauer, J., Schmidt, M. W. I., and Schwark, L.: Plant and soil lipid modification under elevated atmospheric CO2 conditions: II. Stable carbon isotopic values ($\delta ^13$C) and turnover, Org. Geochem., 39(1), 103–117, 2008. Williams, P. M. and Druffel, E. R. M.: Radiocarbon in dissolved organic-matter in the Pacific Ocean, Nature, 330, 246–248, 1987. Witt, M., Fuchser, J., and Koch, B. P.: Fragmentation studies of fulvic acids using collision induced dissociation fourier transform ion cyclotron resonance mass spectrometry, Anal. Chem., 81(7), 2688–2694, 2009. Zonneveld, K. A. F., Bockelmann, F.-D., and Holzwarth, U.: Selective preservation of organic walled dinoflagellate cysts as a tool to quantify past net primary production and bottom water oxygen concentrations, Mar. Geol., 237(3–4), 109–126, doi:10.1016/j.margo.2006.10.023, 2007. Zonneveld, K. A. F., Susek, E., and Fischer, G.: Seasonal variability of the organic-walled dinoflagellate cyst production in the coastal upwelling region off Cape Blanc (Mauritania): a five-year survey, J. Phycol., 46(1), 202–215, 2010. Zonneveld, K. A. F., Chen L., Möbius, J., and Mahmoud, M. S.: Environmental significance of dinoflagellate cysts from the proximal part of the Po-river discharge plume (off southern Italy, Eastern Mediterranean)., J. Sea Res., 62, 189–213, 2009. Zonneveld, K. A. F., Versteegh, G. J. M., and de Lange, G. J.: Preservation of organic walled dinoflagellate cysts in different oxygen regimes: a 10000 years natural experiment, Mar. Micropaleontol., 29, 393–405, 1997. Zonneveld, K. A. F., Versteegh, G. J. M., and Kodrans-Nsiah, M.: Preservation of Late Cenozoic organic-walled dinoflagellate cysts; a review, Mar. Micropaleontol., 86, 179–197, 2008.