Selective preservation of organic matter in marine environments; processes and impact on the sedimentary record

Abstract. 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. 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. 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. 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. 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.

[1]  A. Mix,et al.  Alkenone paleothermometry: Biological lessons from marine sediment records off western South America , 2006 .

[2]  F. Prahl,et al.  Early Diagenesis: Consequences for Applications of Molecular Biomarkers , 1993 .

[3]  A. Mix,et al.  Distribution and composition of organic matter in surface sediments of coastal Southeast Alaska , 2009 .

[4]  P. Grootes,et al.  Complexity of Soil Organic Matter: AMS 14C Analysis of Soil Lipid Fractions and Individual Compounds , 2004, Radiocarbon.

[5]  J. Oades,et al.  Comparative organic geochemistries of soils and marine sediments , 1997 .

[6]  Mea S. Cook,et al.  Evidence from diatom-bound nitrogen isotopes for subarctic Pacific stratification during the last ice age and a link to North Pacific denitrification changes , 2007 .

[7]  J. Hedges,et al.  The characterization of plant tissues by their lignin oxidation products , 1979 .

[8]  F. Prahl,et al.  Annual biomarker record for export production in the central Arabian Sea , 2000 .

[9]  G. Lange,et al.  A natural exposure experiment on short-term species-selective aerobic degradation of dinoflagellate cysts , 2008 .

[10]  S. Kasten,et al.  Active and buried authigenic barite fronts in sediments from the eastern Cape Basin , 2006 .

[11]  Andrew C. Scott,et al.  Studies of Fossil and Modern Spore Wall Biomacromolecules using13C Solid State NMR , 1996 .

[12]  A. Marshall,et al.  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 , 2009 .

[13]  H. Talbot,et al.  Bacterial populations recorded in bacteriohopanepolyol distributions in soils from Northern England , 2008 .

[14]  S. Trumbore,et al.  Comparison of Fractionation Methods for Soil Organic Matter 14C Analysis , 1996, Radiocarbon.

[15]  T. Schaub,et al.  Speciation of Aromatic Compounds in Petroleum Refinery Streams by Continuous Flow Field Desorption Ionization FT-ICR Mass Spectrometry , 2005 .

[16]  S. Kasten,et al.  Processes and Signals of Nonsteady-State Diagenesis in Deep-Sea Sediments and their Pore Waters , 2003 .

[17]  G. Lange,et al.  Geochemical and paleomagnetic evidence for the occurrence of “missing” sapropels in eastern Mediterranean sediments , 1997 .

[18]  Stefan Schouten,et al.  Ongoing Buildup of Refractory Organic Carbon in Boreal Soils During the Holocene , 2006, Science.

[19]  S. Wakeham,et al.  Alteration of alkenone unsaturation ratio with depth in the Black Sea: Potential roles of stereomutation and aerobic biodegradation , 2008 .

[20]  Sunghwan Kim,et al.  Hydrogen Deficient Molecules in Natural Riverine Water Samples - Evidence for the Existence of Black Carbon in DOM , 2004 .

[21]  F. Bockelmann,et al.  Selective preservation of organic-walled dinoflagellate cysts as a tool to quantify past net primary production and bottom water oxygen concentrations , 2007 .

[22]  G. Mollenhauer,et al.  Diagenetic and sedimentological controls on the composition of organic matter preserved in California Borderland Basin sediments , 2007 .

[23]  A. Mangini,et al.  Geochemistry of a piston core from Ontong Java Plateau (western equatorial Pacific): evidence for sediment redistribution and changes in paleoproductivity , 1996 .

[24]  E. Cortijo,et al.  Precessional forcing of productivity in the North Atlantic Ocean , 1998 .

[25]  J. Damsté,et al.  An example of oxidative polymerization of unsaturated fatty acids as a preservation pathway for dinoflagellate organic matter , 2004 .

[26]  F. Prahl,et al.  Selective organic matter preservation in ''burn-down'' turbidites on the Madeira Abyssal Plain , 2003 .

[27]  J. Calvin Giddings,et al.  BIOCHEMICAL DISTRIBUTIONS (AMINO ACIDS, NEUTRAL SUGARS, AND LIGNIN PHENOLS) AMONG SIZE-CLASSES OF MODERN MARINE SEDIMENTS FROM THE WASHINGTON COAST , 1998 .

[28]  Stefan Schouten,et al.  A novel proxy for terrestrial organic matter in sediments based on branched and isoprenoid tetraether lipids , 2004 .

[29]  M. Schmidt,et al.  Plant and soil lipid modification under elevated atmospheric CO2 conditions: II. Stable carbon isotopic values (δ13C) and turnover , 2008 .

[30]  R. Keil,et al.  Influence of organic-mineral aggregates on microbial degradation of the dinoflagellate Scrippsiella trochoidea , 2005 .

[31]  David Bastviken,et al.  Degradation of dissolved organic matter in oxic and anoxic lake water , 2004 .

[32]  Gerald H. Haug,et al.  Isotopic constraints on glacial/interglacial changes in the oceanic nitrogen budget , 2004 .

[33]  Stephen Calvert,et al.  Reduced nitrogen fixation in the glacial ocean inferred from changes in marine nitrogen and phosphorus inventories , 2002, Nature.

[34]  M. Altabet,et al.  The effect of millennial-scale changes in Arabian Sea denitrification on atmospheric CO2 , 2002, Nature.

[35]  A. Dahmke,et al.  Discrete barite particles and barium as tracers of paleoproductivity in south Atlantic sediments , 1994 .

[36]  S. Wakeham,et al.  Settling velocity spectra and the ballast ratio hypothesis , 2009 .

[37]  D. Kroon,et al.  A 300 kyr high-resolution aridity record of the North African continent , 1995 .

[38]  L. Coppola,et al.  The importance of ultrafine particles as a control on the distribution of organic carbon in Washington Margin and Cascadia Basin sediments , 2007 .

[39]  J. Sachs,et al.  Oligotrophy and nitrogen fixation during eastern mediterranean sapropel events , 1999, Science.

[40]  Fabienne Marret-Davies Les effets de l'acétolyse sur les assemblages de kystes de dinoflagellés , 1993 .

[41]  J. Damsté,et al.  The influence of oxic degradation on the sedimentary biomarker record II. Evidence from Arabian Sea sediments , 2002 .

[42]  H. Jenkyns,et al.  Nitrogen isotope evidence for water mass denitrification during the Early Toarcian (Jurassic) oceanic anoxic event , 2001 .

[43]  D. Anderson,et al.  Characterization of a highly resistant biomacromolecular material in the cell wall of a marine dinoflagellate resting cyst , 1998 .

[44]  A. Livingston,et al.  A novel method for characterisation of microbial growth kinetics on volatile organic compounds , 1999, Applied Microbiology and Biotechnology.

[45]  T. Dittmar,et al.  From mass to structure: an aromaticity index for high‐resolution mass data of natural organic matter , 2006 .

[46]  D. Hollander,et al.  Evidence for differential degradation of alkenones under contrasting bottom water oxygen conditions: implication for paleotemperature reconstruction , 1999 .

[47]  T. Dittmar,et al.  Thermogenic organic matter dissolved in the abyssal ocean , 2006 .

[48]  G. Bohrmann,et al.  Barium accumulation in the Atlantic sector of the Southern Ocean: Results From 190,000-year records , 1997 .

[49]  E. Druffel,et al.  Radiocarbon in dissolved organic matter in the central North Pacific Ocean , 1987, Nature.

[50]  M. Simpson,et al.  Evaluation of CuO oxidation parameters for determining the source and stage of lignin degradation in soil , 2006 .

[51]  Stefan Schouten,et al.  The effect of maturity and depositional redox conditions on archaeal tetraether lipid palaeothermometry , 2004 .

[52]  S. Libes,et al.  The isotope geochemistry of particulate nitrogen in the Peru upwelling area and the Gulf of Maine , 1988 .

[53]  M. Torres,et al.  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 , 1996 .

[54]  J. Hayes,et al.  Proceedings of a workshop on alkenone‐based paleoceanographic indicators , 2001 .

[55]  D. Canfield,et al.  Factors influencing organic carbon preservation in marine sediments. , 1994, Chemical geology.

[56]  K. Haider Problems Related to the Humification Processes in Soils of Temperate Climates , 1992 .

[57]  F. Prahl,et al.  Post-depositional stability of long-chain alkenones under contrasting redox conditions , 1989, Nature.

[58]  P. Hatcher,et al.  Survival of Protein in an Organic-Rich Sediment: Possible Protection by Encapsulation in Organic Matter , 1997, Naturwissenschaften.

[59]  John M. Melack,et al.  Transport of organic carbon in the world’s rivers , 1981 .

[60]  M. Schmidt,et al.  Lignin is preserved in the fine silt fraction of an arable Luvisol , 2007 .

[61]  P. Hatcher,et al.  Identification of black carbon derived structures in a volcanic ash soil humic acid by Fourier transform ion cyclotron resonance mass spectrometry. , 2004, Environmental science & technology.

[62]  J. Sarmiento,et al.  Submarine groundwater discharge revealed by 228 Ra distribution in the upper Atlantic Ocean , 2007 .

[63]  T. Stocker,et al.  Four Climate Cycles of Recurring Deep and Surface Water Destabilizations on the Iberian Margin , 2007, Science.

[64]  Klaus Kaiser,et al.  How relevant is recalcitrance for the stabilization of organic matter in soils , 2008 .

[65]  R. Keil,et al.  Changes in organic matter-mineral interactions for marine sediments with varying oxygen exposure times , 2007 .

[66]  J. Hayes,et al.  Spatial and Temporal Offsets Between Proxy Records in a Sediment Drift , 2002, Science.

[67]  Larry A. Chesal,et al.  The structure of marine fulvic and humic acids , 1983 .

[68]  Paul G. Falkowski,et al.  Evolution of primary producers in the sea , 2007 .

[69]  D. Hammond,et al.  Early oxidation of organic matter in pelagic sediments of the eastern equatorial Atlantic: suboxic diagenesis , 1979 .

[70]  Andreas Springer,et al.  Identification of fulvic acids and sulfated and nitrated analogues in atmospheric aerosol by electrospray ionization fourier transform ion cyclotron resonance mass spectrometry. , 2006, Analytical chemistry.

[71]  G. Versteegh,et al.  Use of selective degradation to separate preservation from productivity , 2002 .

[72]  C. Marshall,et al.  Macromolecular composition of the dinoflagellate cyst Thalassiphora pelagica (Oligocene, SW Germany) , 2007 .

[73]  D. Ruderman,et al.  Naphthenic acids as indicators of crude oil biodegradation in soil, based on semi-quantitative electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. , 2008, Rapid communications in mass spectrometry : RCM.

[74]  J. D. Leeuw On the origin of sedimentary aliphatic macromolecules: A comment on recent publications by Gupta et al. , 2007 .

[75]  C. Jeandel,et al.  The marine barite saturation state of the world's oceans , 1999 .

[76]  J. Sharples,et al.  Swimming for survival: A role of phytoplankton motility in a stratified turbulent environment , 2008 .

[77]  J. Middelburg,et al.  Amino acid biogeochemistry and organic matter degradation state across the Pakistan margin oxygen minimum zone , 2009 .

[78]  M. Hanford,et al.  Archaeal tetraether lipids , 2002, Applied biochemistry and biotechnology.

[79]  Erwin Suess,et al.  Particulate organic carbon flux in the oceans—surface productivity and oxygen utilization , 1980, Nature.

[80]  C. Arnosti,et al.  Enzyme activities in the water column and in shallow permeable sediments from the northeastern Gulf of Mexico , 2009 .

[81]  G. Fischer,et al.  SEASONAL VARIABILITY OF THE ORGANIC‐WALLED DINOFLAGELLATE CYST PRODUCTION IN THE COASTAL UPWELLING REGION OFF CAPE BLANC (MAURITANIA): A FIVE‐YEAR SURVEY 1 , 2010 .

[82]  Bernd Marschner,et al.  SOM fractionation methods: Relevance to functional pools and to stabilization mechanisms , 2007 .

[83]  B. Forsberg,et al.  Origins and processing of organic matter in the Amazon River as indicated by carbohydrates and amino acids , 1994 .

[84]  D. Burdige,et al.  Burial of terrestrial organic matter in marine sediments: A re‐assessment , 2005 .

[85]  J. D. Leeuw,et al.  U37K′ values for Isochrysis galbana as a function of culture temperature, light intensity and nutrient concentrations , 2001 .

[86]  J. Damsté,et al.  The influence of oxic degradation on the sedimentary biomarker record , 2002 .

[87]  M. Canals,et al.  Productivity response in the North Canary Basin to climate changes during the last 250 000 yr: a multi-proxy approach , 2002 .

[88]  M. Witt,et al.  Advanced characterization of marine dissolved organic matter by combining reversed-phase liquid chromatography and FT-ICR-MS , 2008 .

[89]  H. Grobe,et al.  Distribution of clay minerals and proxies for productivity in surface sediments of the Bellingshausen and Amundsen seas (West Antarctica) – Relation to modern environmental conditions , 2003 .

[90]  G. Lange,et al.  Biogenic barium and the detrital Ba/Al ratio: a comparison of their direct and indirect determination , 2004 .

[91]  T. Dittmar,et al.  Tools for Studying Biogeochemical Connectivity Among Tropical Coastal Ecosystems , 2009 .

[92]  T. Herbert 6.15 – Alkenone Paleotemperature Determinations , 2003 .

[93]  Matthias Witt,et al.  Molecular characterization of dissolved organic matter in pore water of continental shelf sediments , 2009 .

[94]  G. Bohrmann,et al.  Barium acumulation in the Atlantic sector of the Southern Ocean: Results from 190,00-year records , 1997 .

[95]  M. Witt,et al.  Fragmentation studies of fulvic acids using collision induced dissociation fourier transform ion cyclotron resonance mass spectrometry. , 2009, Analytical chemistry.

[96]  J. S. Sinninghe Damsté,et al.  Aging of marine organic matter during cross‐shelf lateral transport in the Benguela upwelling system revealed by compound‐specific radiocarbon dating , 2007 .

[97]  R. Bol,et al.  Molecular dynamics of organic matter in a cultivated soil. , 2002 .

[98]  M. Witt,et al.  Spectroscopic characterization of fulvic acids extracted from the rock exudate Shilajit , 2008 .

[99]  J. Farrell,et al.  Glacial-interglacial changes in nutrient utilization in the equatorial Pacific Ocean , 1995, Nature.

[100]  M. Lehmann,et al.  Preservation of organic matter and alteration of its carbon and nitrogen isotope composition during simulated and in situ early sedimentary diagenesis , 2002 .

[101]  Stefan Schouten,et al.  Is there evidence for a substantial contribution of prokaryotic biomass to organic carbon in Phanerozoic carbonaceous sediments , 1997 .

[102]  J. Middelburg,et al.  Burial at Sea , 2007, Science.

[103]  Stefan Schouten,et al.  Effects of long term oxic degradation on the U37K′, TEX86 and BIT organic proxies , 2009 .

[104]  R. Evershed,et al.  Experimental evidence for the formation of geomacromolecules from plant leaf lipids. , 2007 .

[105]  G. Lange,et al.  Preservation of organic-walled dinoflagellate cysts in different oxygen regimes: a 10,000 year natural experiment , 1997 .

[106]  R. Parkes,et al.  Microbial degradation of the marine prymnesiophyte Emiliania huxleyi under oxic and anoxic conditions as a model for early diagenesis: long chain alkadienes, alkenones and alkyl alkenoates , 1998 .

[107]  Peter A. Jumars,et al.  Burrowing mechanics: Burrow extension by crack propagation , 2005, Nature.

[108]  S. Kasten,et al.  Different nutrient sources forcing increased productivity during eastern Mediterranean S1 sapropel formation as reflected by calcareous dinoflagellate cysts , 2004 .

[109]  S. Wakeham,et al.  Molecular indicators of diagenetic status in marine organic matter , 1997 .

[110]  G. Eglinton,et al.  Radiocarbon Dating of Aliphatic Hydrocarbons A New Approach for Dating Passive-Fraction Carbon in Soil Horizons , 1999 .

[111]  J. Rethemeyer,et al.  Selective preservation of organic matter in marine environments – processes and impact on the fossil record , 2009 .

[112]  N. Blair,et al.  Carbon remineralization in the Amazon–Guianas tropical mobile mudbelt: A sedimentary incinerator , 2006 .

[113]  R. Bidigare,et al.  Controls on the molecular distribution and carbon isotopic composition of alkenones in certain haptophyte algae , 2001 .

[114]  O. Spaargaren,et al.  Occurrence and distribution of tetraether membrane lipids in soils : Implications for the use of the TEX86 proxy and the BIT index , 2006 .

[115]  E. Suess,et al.  Barium in Deep‐Sea Sediment: A Geochemical Proxy for Paleoproductivity , 1992 .

[116]  J. Bishop The barite-opal-organic carbon association in oceanic particulate matter , 1988, Nature.

[117]  Sunghwan Kim,et al.  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 , 2006 .

[118]  J. Damsté,et al.  Sulphidic Mediterranean surface waters during Pliocene sapropel formation , 1999, Nature.

[119]  F. Hu,et al.  Sedimentary organic matter preservation : A test for selective degradation under oxic conditions , 1999 .

[120]  P. Schmitt‐Kopplin,et al.  Characterization of a major refractory component of marine dissolved organic matter , 2006 .

[121]  J. Damsté,et al.  Analysis, structure and geochemical significance of organically-bound sulphur in the geosphere : state of the art and future research , 1990 .

[122]  G. Lange,et al.  REVIEW OF RECENT ADVANCES IN THE INTERPRETATION OF EASTERN MEDITERRANEAN SAPROPEL S1 FROM GEOCHEMICAL EVIDENCE , 1999 .

[123]  R. Keil,et al.  Organic–mineral interactions in marine sediments studied using density fractionation and X-ray photoelectron spectroscopy , 2001 .

[124]  Stefan Schouten,et al.  The lycopane/C31 n-alkane ratio as a proxy to assess palaeoxicity during sediment deposition , 2003 .

[125]  S. Wakeham,et al.  Molecular evidence for degradation and preservation of organic matter in the anoxic Black Sea Basin , 1994 .

[126]  C. Largeau,et al.  A Review of Macromolecular Organic Compounds That Comprise Living Organisms and Their Role in Kerogen, Coal, and Petroleum Formation , 1993 .

[127]  G. Versteegh,et al.  Resistant macromolecules of extant and fossil microalgae , 2004 .

[128]  A. Heiskanen,et al.  Sexuality and cyst formation of the spring-bloom dinoflagellate Scrippsiella hangoei in the coastal northern Baltic Sea , 1999 .

[129]  M. Gough,et al.  Terrestrial plant biopolymers in marine sediments , 1993 .

[130]  C. Slomp,et al.  Synchronous basin-wide formation and redox-controlled preservation of a Mediterranean sapropel , 2008 .

[131]  Hilairy E. Hartnett,et al.  Influence of oxygen exposure time on organic carbon preservation in continental margin sediments , 1998, Nature.

[132]  G. Schmiedl,et al.  Late Pleistocene sedimentation in the Western Mediterranean Sea: implications for productivity changes and climatic conditions in the catchment areas , 2003 .

[133]  R. Schneider,et al.  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 200,000 years , 1997 .

[134]  S. Wakeham,et al.  Lipid biomarker fluxes in the Arabian Sea, with a comparison to the equatorial Pacific Ocean , 2002 .

[135]  A. Pearson,et al.  The origin of n-alkanes in Santa Monica Basin surface sediment: a model based on compound-specific Δ14C and δ13C data , 2000 .

[136]  R. Schneider,et al.  Climatic controls on central African hydrology during the past 20,000 years , 2005, Nature.

[137]  M. Altabet Constraints on oceanic N balance/imbalance from sedimentary 15 N records , 2006 .

[138]  R. Macdonald,et al.  The supply and preservation of ancient and modern components of organic carbon in the Canadian Beaufort Shelf of the Arctic Ocean , 2005 .

[139]  Gerhard Kattner,et al.  Fundamentals of molecular formula assignment to ultrahigh resolution mass data of natural organic matter. , 2007, Analytical chemistry.

[140]  C. Heip,et al.  Spatial distribution of detrital resources determines the outcome of competition between bacteria and a facultative detritivorous worm , 2009 .

[141]  M. Voss,et al.  Records of southern and central Baltic Sea eutrophication in δ 13 C and δ 15 N of sedimentary organic matter , 2000 .

[142]  G. Versteegh,et al.  Preservation and organic chemistry of Late Cenozoic organic-walled dinoflagellate cysts: A review , 2008 .

[143]  J. Grimalt,et al.  Evidence for enhanced Mediterranean thermohaline circulation during rapid climatic coolings , 2000 .

[144]  Stefan Schouten,et al.  Selective preservation of soil organic matter in oxidized marine sediments (Madeira Abyssal Plain) , 2008 .

[145]  O. Marchal,et al.  Variations of oxygen-minimum and primary productivity recorded in sediments of the Arabian Sea , 1999 .

[146]  Gerhard Kattner,et al.  Molecular formulae of marine and terrigenous dissolved organic matter detected by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry , 2005 .

[147]  C. Chenu,et al.  Carbon-13 natural abundance as a tool to study the dynamics of lignin monomers in soil : an appraisal at the Closeaux experimental field (France) , 2005 .

[148]  S. Kasten,et al.  Reconstruction of primary productivity from the barium contents in surface sediments of the South Atlantic Ocean , 2001 .

[149]  C. Heip,et al.  Bioturbation: a fresh look at Darwin's last idea. , 2006, Trends in ecology & evolution.

[150]  J. Damsté,et al.  Postdepositional oxic degradation of alkenones : implications for the measurement of palaeo sea surface temperatures , 1998 .

[151]  I. Kögel‐Knabner,et al.  Contribution of lignin and polysaccharides to the refractory carbon pool in C-depleted arable soils , 2003 .

[152]  G. Eglinton,et al.  Molecular stratigraphy: a new tool for climatic assessment , 1986, Nature.

[153]  D. Canfield,et al.  Towards a consistent classification scheme for geochemical environments, or, why we wish the term ‘suboxic’ would go away , 2009, Geobiology.

[154]  R. Glud Oxygen dynamics of marine sediments , 2008 .

[155]  R. Grieken,et al.  Barite formation in the Southern Ocean water column , 1991 .

[156]  D. Sarno,et al.  Dinoflagellate cyst production at a coastal Mediterranean site , 1998 .

[157]  Thomas S. Bianchi,et al.  Temporal variability in terrestrially-derived sources of particulate organic carbon in the lower Mississippi River and its upper tributaries , 2007 .

[158]  J. Fry,et al.  A quantitative study of microbial decomposition of biopolymers in Recent sediments from the Peru Margin , 1993 .

[159]  J. Thomson,et al.  Modification and complete removal of eastern Mediterranean sapropels by postdepositional oxidation , 1994 .

[160]  G. Fischer,et al.  Nitrogen Isotopes in Sinking Particles and Surface Sediments in the Central and Southern Atlantic , 2003 .

[161]  F. Dehairs,et al.  DISCRETE SUSPENDED PARTICLES OF BARITE AND THE BARIUM CYCLE IN THE OPEN OCEAN , 1980 .

[162]  M. Emmett,et al.  Molecular characterization of petroporphyrins in crude oil by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry , 2001 .

[163]  A. Marshall,et al.  Fourier transform ion cyclotron resonance mass spectrometry: a primer. , 1998, Mass spectrometry reviews.

[164]  A. Taniguchi,et al.  Contribution of benthic cysts to the population dynamics of Scrippsiella spp , 1996 .

[165]  A. Gooday,et al.  Intracellular Barite Crystals in Two Xenophyophores, Aschemonella Ramuliformis and Galatheammina Sp. (Protozoa: Rhizopoda) With Comments on the Taxonomy of A. Ramuliformis , 1982, Journal of the Marine Biological Association of the United Kingdom.

[166]  F. Mackenzie,et al.  Comparison of anaerobic and aerobic biodegradation of mineralized skeletal structures in marine and estuarine conditions , 1994 .

[167]  P. Sollins,et al.  Stabilization and destabilization of soil organic matter: mechanisms and controls , 1996 .

[168]  J. Hopkins Post‐depositional palynomorph degradation in quaternary shelf sediments: A laboratory experiment studying the effects of progressive oxidation , 2002 .

[169]  C. Heip,et al.  Ecology of estuarine macrobenthos , 1999 .

[170]  J. Farrell,et al.  Glacialá¤-interglacial changes in nutrient utilization in the equatorial Pacific Ocean , 1995, Nature.

[171]  T. J. Chow,et al.  On the marine geochemistry of barium , 1960 .

[172]  K. Zonneveld,et al.  Environmental significance of dinoflagellate cysts from the proximal part of the Po-river discharge plume (off southern Italy, Eastern Mediterranean) , 2009 .

[173]  A. Mangini,et al.  WHY SOME MEDITERRANEAN SAPROPELS SURVIVED BURN-DOWN (AND OTHERS DID NOT) , 1997 .

[174]  Robert G. Hilton,et al.  Tropical-cyclone-driven erosion of the terrestrial biosphere from mountains , 2008 .

[175]  A. Marshall,et al.  Exact masses and chemical formulas of individual Suwannee River fulvic acids from ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectra. , 2003, Analytical chemistry.

[176]  F. Marret,et al.  Atlas of modern organic-walled dinoflagellate cyst distribution , 2003 .

[177]  Michael A. Freitas,et al.  The application of electrospray ionization mass spectrometry (ESI MS) to the structural characterization of natural organic matter , 2002 .

[178]  P. Mudie,et al.  Marine palynology: potentials for onshore—offshore correlation of Pleistocene—Holocene records , 2006 .

[179]  J. Hedges,et al.  Sedimentary organic matter preservation: an assessment and speculative synthesis , 1995 .

[180]  R. Collier,et al.  The trace element geochemistry of marine biogenic particulate matter , 1980 .

[181]  C. Vargas,et al.  Origin and Evolution of Coccolithophores: From Coastal Hunters to Oceanic Farmers , 2007 .

[182]  Biomacromolecules of Algae and Plants and their Fossil Analogues , 2006 .

[183]  L. Lourens,et al.  The formation of Pliocene sapropels and carbonate cycles in the Mediterranean: Diagenesis, dilution, and productivity , 1994 .

[184]  S. Kasten,et al.  Biogenic barium as a proxy for paleoproductivity: Methods and limitations of application , 1999 .

[185]  R. Ganeshram,et al.  An experimental investigation of Barite formation in seawater , 2003 .

[186]  C. Ekberg,et al.  Relationship between planktonic dinoflagellate abundance, cysts recovered in sediment traps and environmental factors in the Gullmar Fjord, Sweden , 2001 .

[187]  C. Masiello,et al.  Controls on black carbon storage in soils , 2007 .

[188]  E. Goldberg,et al.  Chemistry of Pacific pelagic sediments , 1958 .

[189]  R. Benner,et al.  Distribution and cycling of terrigenous dissolved organic matter in the ocean , 1997, Nature.

[190]  P. Grootes,et al.  LIPID FRACTIONS AND INDIVIDUAL COMPOUNDS , 2004 .

[191]  L. Goeyens,et al.  Suspended barite as a tracer of biological-activity in the southern-ocean , 1991 .

[192]  J. Hedges,et al.  Organic geochemical perspectives on estuarine processes: sorption reactions and consequences , 1999 .

[193]  O. Tendal A monograph of the Xenophyophoria (Rhizopodea, Protozoa) , 1972 .

[194]  V. Ramaswamy,et al.  Stable nitrogen isotopic ratios of sinking particles and sediments from the northern Indian Ocean , 2005 .

[195]  R. Sleighter,et al.  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 , 2008 .

[196]  F. Prahl,et al.  A biomarker perspective on prymnesiophyte productivity in the northeast pacific ocean , 1993 .

[197]  Stefan Schouten,et al.  An experimental field study to test the stability of lipids used for the TEX86 and UK'37 palaeothermometers , 2009 .

[198]  F. Prahl Prospective use of molecular paleontology to test for iron limitation on marine primary productivity , 1992 .

[199]  A. Mennito,et al.  Observation of vanadyl porphyrins and sulfur-containing vanadyl porphyrins in a petroleum asphaltene by atmospheric pressure photonionization Fourier transform ion cyclotron resonance mass spectrometry. , 2008, Rapid communications in mass spectrometry : RCM.

[200]  R. Ganeshram,et al.  Glacial-interglacial variability in denitrification in the World's Oceans: Causes and consequences , 2000 .

[201]  P. Hatcher,et al.  Sequestration of organic nitrogen in the sapropel from Mangrove Lake, Bermuda , 2001 .

[202]  P. Bonin,et al.  Degradation of alkenones by aerobic heterotrophic bacteria: Selective or not? , 2008 .

[203]  G. C. Klein,et al.  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 , 2004 .

[204]  G. Schmiedl,et al.  Spatial productivity variations during formation of sapropels S5 and S6 in the Mediterranean Sea: evidence from Ba contents , 2001 .

[205]  C. Heip,et al.  Linking diagenetic alteration of amino acids and bulk organic matter reactivity , 1999 .

[206]  C. Heip,et al.  Similar rapid response to phytodetritus deposition in shallow and deep-sea sediments , 2005 .

[207]  S. Kasten,et al.  Barium peaks at glacial terminations in sediments of the equatorial Atlantic Ocean—relicts of deglacial productivity pulses? , 2001 .

[208]  J. Bauer,et al.  14C activity of dissolved organic carbon fractions in the north-central Pacific and Sargasso Sea , 1992, Nature.

[209]  M. Krom,et al.  Active post-depositional oxidation of the most recent sapropel (S1) in sediments of the eastern Medi , 1996 .

[210]  C. Chenu,et al.  Lignin turnover kinetics in an agricultural soil is monomer specific , 2006 .

[211]  M. Altabet,et al.  The Use of Nitrogen Isotopic Ratio for Reconstruction of Past Changes in Surface Ocean Nutrient Utilization , 1994 .

[212]  G. Lange,et al.  Redistribution and geochemical behaviour of redox-sensitive elements around S1, the most recent eastern Mediterranean sapropel , 1995 .

[213]  R. Byrne,et al.  Morphologies and transformations of celestite in seawater: The role of acantharians in strontium and barium geochemistry , 1992 .

[214]  J. Guerra-García,et al.  Oxygen levels versus chemical pollutants: do they have similar influence on macrofaunal assemblages? A case study in a harbour with two opposing entrances. , 2005, Environmental pollution.

[215]  G. Haug,et al.  Glacial/interglacial variations in production and nitrogen fixation in the Cariaco Basin during the last 580 kyr , 1998 .

[216]  S. Honjo,et al.  Biogenic barium fluxes to the deep sea: Implications for paleoproductivity reconstruction , 1995 .

[217]  R. Evershed,et al.  The molecularly-uncharacterized component of nonliving organic matter in natural environments , 2000 .