Geobiology 2007 Lecture 10 The Biogeochemical Carbon Cycle

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1 Geobiology 2007 Lecture 10 The Biogeochemical Carbon Cycle Readings: Assigned Reading: Stanley Chapter 10, pp Kump et al., Chap. 7 Hayes, J. M., Strauss, H. & Kaufman, A. J.., The abundance of 13C in marine organic matter and isotopic fractionation in the global biogeochemical cycle of carbon during the past 800 Ma Chem. Geol. 161, Kerr R.A The story of O2. News focus article from Science 308, 1730 (MIT Server) Catling et al., Astrobiology 5, 415 Other readings: Logan G.A., Hayes J.M., Hieshima G.B. and Summons R.E., 1995, Terminal Proterozoic reorganisation of biogeochemical cycles. Nature 376, Rothman D. H., Hayes J. M., and Summons R. E., 2003, Dynamics of the Neoproterozoic carbon cycle. Proceedings of the National Academy of Science (USA) 100, Acknowledgements: John Hayes and Dan Rothman who provided figures used in this lecture

2 Geobiology 2006 Lecture 9 The Biogeochemical Carbon Cycle Need to know: Elements of the geological C-cycle and exogenic or biological (ocean/atm/biology) C-cycle that affect carbon burial Idealized redox structure of the surface environment Concept of mass balance and use of isotopic data to model C-cycle over different timescales What this tells us about progressive oxygenation of the crust/atm/ocean Excursions in the δ 13 C record of inorganic carbon, concept of oxidation events and significance for biology

3 Geobiology 2006 Lecture 9 The Biogeochemical Carbon Cycle Isotopes are fractionated during chemical and physical equilibrations and during enzyme mediated reactions Patterns in the distributions of C, H, N, S &O isotopic tracers can be related to uptake mechanisms (assimilation), energy-yielding redox reactions (dissimilation) and biosynthetic processes Patterns in the distributions of C, H, N, S &O isotopic tracers in rocks can be understood by analogies to modern processes

5 Courtesy Sam Gon III. Image from Wikimedia Commons,

6 Life s s History on Earth Prokaryote World 1 Multi-cell Life 0.1 Humans P O 2 (atm) First Eukaryotes GOE First Invertebrates Time before Present (Ga)

9 JM Hayes Courtesy John Hayes. Used with permission.

10 JM Hayes Courtesy John Hayes. Used with permission.

11 Isotopic Mass Balance of Crustal Carbon Reservoirs Microorganisms Carbon Input Kinetic Isotope Effect = CO 2 HCO3 0.2 Reduced Carbon 0.8 Carbonate δ 13 C -10 Crustal Average 0 10 Courtesy of Dave Des Marais, NASA Ames. Used with permission. (Des Marais, 2002)

12 Rothman et al., 2005 Courtesy of Dan Rothman. Used with permission.

13 Image removed due to copyright restrictions. Please see Fig. 2 in Shields, Graham, and Veizer, Ján. Precambrian marine carbonate isotope database: Version 1.1. Geochemistry Geophysics Geosystems 3 (June 6, 2002): 12 pages. Rothman et al., 2005 Courtesy of Dan Rothman. Used with permission.

14 JM Hayes Courtesy John Hayes. Used with permission. Courtesy of Elsevier, Inc., Used with permission. Marine Isotopic Signals 800Ma-present

15 Courtesy of Dan Rothman. Used with permission.

16 δ i ε f JM Hayes Courtesy John Hayes. Used with permission.

17 JM Hayes Courtesy John Hayes. Used with permission.

18 Marine Isotopic Signals 150Ma-present JM Hayes Courtesy John Hayes. Used with permission. Courtesy Elsevier, Inc., Used with permission.

19 Courtesy of Dan Rothman. Used with permission.

Massive Mesozoic-Cenozoic Plankton Deposits Seven

Image from Wikimedia Commons, http://commons.

White Cliffs of Dover Courtesy NASA Diatomaceous

20 Massive Mesozoic-Cenozoic Plankton Deposits Seven Sisters Fossils (East Sussex) Chl a+c Phytoplankton Diatoms Dinoflagellates Coccolithophorids Courtesy Dan Taylor. Image from Wikimedia Commons, White Cliffs of Dover Courtesy NASA Diatomaceous Earth Mine, Kenya Courtesy Adrian Barnes SeaWiFS views a phytoplankton bloom near the Grand Banks of Newfoundland. J Waldbauer

21 So, how did it all start? JM Hayes Courtesy John Hayes. Used with permission.

22 Biogeochemical C Cycles before O 2 Photosynthesis Fluxes, x Moles per Year? ~40 Fresh Organic Matter Sedimentary Organic Matter ~40-? CO 2: Sea,Atm. >20 Marine HCO 3 - Carbonates >15 Cycle Timescales, years Metamorphic and Igneous Reduced Carbon 4 20 Mantle Carbon Marble Courtesy of Dave Des Marais, NASA Ames. Used with permission.

23 Biogeochemical Carbon Cycle Fluxes, x 1012 Moles per Year Fresh Organic Matter Sedimentary Organic Matter Metamorphic and Igneous Reduced Carbon CO 2: Sea,Atm Mantle Carbon Marine HCO 3 - Carbonates Marble 1.6 Cycle Timescales, years C Courtesy of Dave Des Marais, NASA Ames. Used with permission. (Des Marais, 2001)

24 JM Hayes Courtesy John Hayes. Used with permission.

25 JM Hayes Courtesy John Hayes. Used with permission.

26 Life s s History on Earth Prokaryote World 1 Multi-cell Life 0.1 Humans P O 2 (atm) First Eukaryotes First Invertebrates Dinosaurs Time before Present (Ga)

27 Carbon Isotopic Record in Sedimentary Carbonates and Organic Matter δ 13 C * -3.0 Oxidized Paleosols Age, Ga -2.0 BIF Disappear Courtesy of Dave Des Marais, NASA Ames. Used with permission Carbonates Organics (Des Marais, 2001)

28 C-Cycle Models; Des Marais et al., 1992, Carbon Isotopic Evidence for Stepwise Oxidation of the Proterozoic Environment. Nature 359, 605 ε p for well-preserved organic matter In steady state, and assuming δ ~ δa Image removed due to copyright restrictions. Please see Fig. 2 in Des Marais, David J., et al. Carbon Isotope Evidence for the Stepwise Oxidation of the Proterozoic Environment. Nature 359 (October 15, 1992): δ i = f * δ o (1-f) δ o δ a = δ i + f * ε and modeled using a moving 30Ma window

29 C-Cycle Models; Des Marais et al., 1992, Carbon Isotopic Evidence for Stepwise Oxidation of the Proterozoic Environment. Nature 359, 605 Image removed due to copyright restrictions. Please see Fig. 3 in Des Marais, David J., et al. Carbon Isotope Evidence for the Stepwise Oxidation of the Proterozoic Environment. Nature 359 (October 15, 1992): and modeled using a 200 or 100 Ma running average evidence for changes in f over time

30 C-Cycle Models; Des Marais et al., 1992, Carbon Isotopic Evidence for Stepwise Oxidation of the Proterozoic Environment. Nature 359, 605 Image removed due to copyright restrictions. Please see Fig. 4 in Des Marais, David J., et al. Carbon Isotope Evidence for the Stepwise Oxidation of the Proterozoic Environment. Nature 359 (October 15, 1992): Evidence for an increasing crustal inventory of C org

31 Major Divisions of Earth History I II III Archean Proterozoic Phanerozoic Ocean Redox Solar System Formation Late Heavy Bombardment po 2 < po 2 > 0.03 po 2 > 0.2 bar bar bar ferrous oceans cyanobacteria Earlier Snowball Episodes sulfidic oceans algae, protists Later Snowball Episodes oxic oceans complex animals & plants States through Time Figure by MIT OCW. The first order approximation Image removed due to copyright restrictions. Please see Fig. 2 in Shields, Graham, and Veizer, Ján. Precambrian Marine Carbonate Isotope Database: Version 1.1. Geochemistry Geophysics Geosystems 3 (June 6, 2002): 12 pages.

32 JM Hayes Marine Isotopic Signals 800Ma-present Courtesy John Hayes. Used with permission.

33 Courtesy of Dan Rothman. Used with permission.

34 δa (inorganic carbon) for the past 800Ma (Hayes et al., 1999)

35 Courtesy of Dan Rothman. Used with permission.

36 Courtesy of Dan Rothman. Used with permission.

37 Steady State Carbon Burial Model δ i weathering volcanism δ Ocean δ a δ o Sediment In steady state, and assuming δ ~ δa δ i = f * δ o (1-f) δ o δ a = δ i + f * ε Where ε = δ a Courtesy of Dan Rothman. Used with permission. δ o

38 A Carbon Cycle with Two Timescales δ i weathering volcanism inorganic-c δ 2 ε δ 1, τ 1 δ 2, τ 2 δ 2 δ δ a o organic-c Ocean Sediment Courtesy of Dan Rothman. Used with permission.

39 A Carbon Cycle with Two Timescales δ i weathering volcanism inorganic-c δ 2 ε δ 1, τ 1 δ 2, τ 2 δ 2 δ δ a o organic-c Ocean Sediment Courtesy of Dan Rothman. Used with permission.

40 A Carbon Cycle with Two Timescales δ 2 ε δ i δ 1, τ 1 δ 2, τ 2 weathering, volcanism δ 2 δ a carbonate carbon δo organic carbon Courtesy of Dan Rothman. Used with permission.

41 Courtesy of Dan Rothman. Used with permission.

42 A Biogeochemical Model of the Proterozoic Ocean Image removed due to copyright restrictions. Please see Fig. 3a in Logan, Graham A., et al. Terminal Proterozoic Reorganization of Biogeochemical Cycles. Nature 376 (July 6, 1995):

43 After Ventilation Image removed due to copyright restrictions. Please see Fig. 3b in Logan, Graham A., et al. Terminal Proterozoic Reorganization of Biogeochemical Cycles. Nature 376 (July 6, 1995):

44 Text removed due to copyright restrictions. Please see Julian Cribb, Faeces rain spawned humans, The Australian, July 7, and Deborah Smith, Scientists May Have Found the Origin of the Faeces, The Sydney Morning Herald, July 7, 1995.

45 JM Hayes Courtesy John Hayes. Used with permission.

46 δ 13 C limestones Carbon Isotopic Excursions Ma δ 13 C marine organic matter More complete sediment record + Improved chronology 13C fractionation ε TOC 750 Ma 720 Ma 580 Ma f organic-c buried = More detailed picture showing abrupt and extreme C-isotopic shifts Courtesy of Dan Rothman. Used with permission. Sturtian glacial(s) Marinoan/Varanger glacial(s) Image courtesy of Elsevier, Inc., Used with permission.

47 Stratigraphic thickness (common scale except arbitrary for glaciation) Arthropods Ediacara Spiny plankton δ 13 C (VPDB) Cambrian Vendian Marinion Glaciation Sturtian Glaciation Varanger Glaciation 531 U-Pb ages (Ma) _ _ _ 1 580? _ _ 4 +_ Seawater proxy δ 13 C carb Ma Morocco Adoudounian Formation Magaritz et al. (1991) A.C. Maloof (unpubl.) Siberia Turkut Formation Bartley et al. (1998) Namibia Nama Group Saylor et al. (1998) Australia Wonoka Formation Calver (2000) Oman Huqf Group - Shuram Fm Burns and Matter (1993) Namibia Otavi Group Halverson and Hoffman (2003) Namibia Gariep Group Folling " and Frimmel (2002) Svaibard Akademikerbreen Group Halverson (2003) Australia Bitter Springs Formation Hill and Walter (2000) Composite carbon isotopic curve for the Neoproterozoic compared to glacial intervals and absolute geochronology Compilation modified from Halverson (2003: in prep.) Figure by MIT OCW.

48 Paradigm The C-cycle has evolved radically through time Prior to 2.2 Ga anaerobic prokaryotes dominated; wide spread of δ org (δo) values; oxygenic photosynthesis extant but oxygen remained low as sinks >> sources Mantle may have been an important sink for oxidising power (Cloud/Holland) Extreme δ carb (δa) values around 2.2 Ga probably signify the GOE and rise to prominence of aerobes; Decreased spread of δorg (δa) values may reflect dominance of aerobic autotrophs and reductive pentose (Benson-Calvin; C3) cycle

49 Paradigm Although ample evidence for aerobes, the abundance of O 2 in atm and ocean remained low (sulfidic ocean) until another major oxidation event caused a second reorganization In the Neoproterozoic. This was also signified by extreme δa fluctuations. The Neoproterozoic reorganization led to po 2 rising to near PAL allowing animals to flourish and stabilizing the new regime (Hayes, Rothman, Summons et al.) Environmental evolution reflected changes in the balance between thermal, crustal, atmospheric & biological processes

50 Fig. 1 in Fike, D. A., et al. "Oxidation of the Ediacaran Ocean." Nature 444 (December 7, 2006): Courtesy of Nature. Used with permission.

51 JM Hayes Phanerozoic coupling of C- and S-cycles Courtesy John Hayes. Used with permission.

52 JM Hayes Phanerozoic coupling of C- and S-cycles Courtesy John Hayes. Used with permission.

53 Fractionation of C-Isotopes during Autotrophy Pathway, enzyme React & substr Product ε Organisms C Rubisco1 Rubisco2 PEP carboxylase PEP carboxykinase CO 2 +RUBP CO 2 +RUBP HCO - 3 +PEP CO 2 +PEP 3-PGA x 2 3-PGA x 2 oxaloacetate oxaloacetate C4 and CAM 2-15 PEP carboxylase Rubisco1 HCO - 3 +PEP CO 2 +RUBP oxaloacetate 3-PGA x plants & algae cyanobacteria plants & algae plants & algae plants & algae (C4) Acetyl-CoA bacteria CO dehydrog CO 2 + 2H+ CoASH AcSCoA 52 Pyruvate synthase CO2 + Ac-CoA pyruvate PEP carboxylase HCO - 3 +PEP oxaloacetate 2 PEP carboxykinase CO 2 +PEP Oxaloacetate Reductive or reverse TCA CO2 + succinyl- CoA (+ others) α- ketoglutarate 4-13 Bacteria esp green sulfur 3-hydroxypropionate HCO 3- + acetylcoa Malonyl-CoA Green non-s

54 10 Reduct ive TCA Cycle Hydroxypropionat e Cycle Number of Taxa 0 10 Reductive Pentose Phosphate Cycle 0 10 Reductive Acetyl CoA Pathway Δδ C Courtesy of Dave Des Marais, NASA Ames. Used with permission. Compiled by C. House

55 JM Hayes Courtesy John Hayes. Used with permission.

56 JM Hayes Isotopic Relativities Courtesy John Hayes. Used with permission. Courtesy of Elsevier, Inc., Used with permission.

57 JM Hayes Courtesy John Hayes. Used with permission.

58 JM Hayes Courtesy John Hayes. Used with permission.

59 Total Global Bacteria: 4-6 x Cells 15 Elemental Inventories, 10 g Bacteria Terrestrial plants Bacteria/Plants C N P Location Soil Terrestrial Subsurface Open Ocean Oceanic Subsurface Number Division Percentage Cells Time, yrs of Total Figure by MIT OCW.

60 JM Hayes Courtesy John Hayes. Used with permission.

61 JM Hayes Courtesy John Hayes. Used with permission.

The Biogeochemical Carbon Cycle: CO 2,the greenhouse effect, & climate feedbacks. Assigned Reading: Kump et al. (1999) The Earth System, Chap. 7.

The Biogeochemical Carbon Cycle: CO 2,the greenhouse effect, & climate feedbacks Assigned Reading: Kump et al. (1999) The Earth System, Chap. 7. Overhead Transparencies Faint Faint Young Sun Paradox Young