Geobiology 2007 Mass Extinctions in the Geological Record

Geobiology 2007 Lectures 13 & 14- Mass Extinctions in the Geological Record

Carbon Cycle Dynamics and Importance of Timescales virtually all mass extinctions are accompanied by carbon isotopic ‘excursions’ or anomalies indicating disruption of the biogeochemical carbon cycle. An extinction at the Precambrian-Cambrian Boundary??? Biocomplexity was not fully developed so, although the Cambrian Radiation is undisputed, the existence of an extinction beforehand is The Devonian Event (Frasnian-Famennian) in passing The Permian Triassic Boundary (PTB) C-isotopic anomalies, possible mechanisms of extinction

The Paleocene Eocene Boundary (PEB) or Late Paleocene Thermal Maximum C-isotopic anomalies, evidence for temperature changes, extinction

The K-T Extinction (Cretaceous Boundary Event) An impact-related phenomenon?? Readings and Sources • A. D. Anbar A. H. Knoll, Proterozoic Ocean Chemistry and Evolution: A Bioinorganic Bridge? Science 2002:Vol. 297, 1137 - 1142 • Erwin D.H. (1994) The Permo-Triassic Extinction Nature 367, 231-236 • A.H. Knoll, R. K. Bambach, D. E. Canfield, J. P. Grotzinger (1996) Comparative Earth History and Late Permian Mass Extinction Science 273, 455. • Erwin D.H. (1996) The Mother of Mass Extinctions Scientific American 275, 72-78. • Erwin D.H. (2006) Extinction, Princeton Other Readings and Sources • Bedout: A Possible End-Permian Impact Crater Offshore of Northwestern Australia L. Becker, R. J. Poreda, A. R. Basu, K. O. Pope, T. M. Harrison, C. Nicholson, and R. Iasky Science 4 June 2004; 304: 1469-1476; published online 13 May 2004

• Photic Zone Euxinia During the Permian-Triassic Superanoxic Event Kliti Grice, Changqun Cao, Gordon D. Love, Michael E. Böttcher, Richard J. Twitchett, Emmanuelle Grosjean, Roger E. Summons, Steven C. Turgeon, William Dunning, and Yugan Jin Science 4 February 2005; 307: 706-709; published online 20 January 2005 • Sulfide hypothesis of Lee Kump: Kump, Pavlov and Arthur, Geology 33 (May) 2005 Need to Know • Nature of evidence for mass extinctions • Names and ages of five mass extinctions – Importance of geochronology • Which ones attributed to ‘extrterrestrial’ causes and why • Those which are matched to geobiological hypotheses – Types of geobiological evidence (isotopes, evidence of euxinia, climate change and the characteristics of these at events) Major Divisions of Earth History I II III Earth’s Surface Archean Proterozoic Phanerozoic

pO < 0.002 pO2 > 0.03 Redox vs Time 2 pO2 > 0.2 bar bar bar

ferrous sulfidic oxic oceans oceans oceans Later Snowball Episodes cyano- Earlier Snowball Episodes algae, complex Solar System Formation bacteria protists animals

Late Heavy Bombardment & plants

5.0 4.0 3.0 2.0 1.0 0.0

Figure by MIT OCW. Intervals between Redox stages marked by putative Snowball Image removed due to copyright restrictions. Episodes and Extreme Isotopic Please see Fig. 2 in Shields, Graham, and Veizer, Ján. “Precambrian Marine Carbonate Excursions Isotope Database: Version 1.1.” Geochemistry Geophysics Geosystems 3 (June 6, 2002): 12 pages. Anbar and Knoll, 2002 Text removed due to copyright restrictions. Please see Abstract in Anbar, A. D., and Knoll, A. H. “Proterozoic Ocean Chemistry and Evolution: A Bioinorganic Bridge?” Science 297 (August 16, 2002): 1137-1142. Image removed due to copyright restrictions. Please see Fig. 1 in Anbar, A. D., and Knoll, A. H. “Proterozoic Ocean Chemistry and Evolution: A Bioinorganic Bridge?” Science 297 (August 16, 2002): 1137-1142. Image removed due to copyright restrictions. Please see Fig. 2 in Anbar, A. D., and Knoll, A. H. “Proterozoic Ocean Chemistry and Evolution: A Bioinorganic Bridge?” Science 297 (August 16, 2002): 1137-1142. δ13C (VPDB) Seawater proxy δ13C -10 -5 0 5 10 carb 1000 531 850-530 Ma U-Pb ages Morocco

Arthropods Global Compilation of Late Cambrian (Ma) Adoudounian Formation Magaritz et al. (1991) Neoproterozoic Carbon 0 Vendian 543.3 + _ 1 A.C. Maloof (unpubl.) Isotope Excursions and their 545.1 + _ 1 Siberia Relationships to Glaciations

Ediacara Turkut Formation _ 548.1 + 1 Bartley et al. (1998) Namibia Varanger Glaciation 580? Nama Group Saylor et al. (1998) Australia Wonoka Formation

Spiny plankton Calver (2000) Oman Huqf Group - Shuram Fm Burns and Matter (1993) Namibia Marinion Glaciation 650 Otavi Group Halverson and Hoffman (2003) Stratigraphic thickness Namibia Sturtian Glaciation _ Gariep Group 746 + 2 " 758 + _ 4 Folling and Frimmel (2002) (common scale except arbitrary for glaciation) (common scale except arbitrary Svaibard Akademikerbreen Group Halverson (2003) Australia 827 + _ 6 Bitter Springs Formation Hill and Walter (2000)

Compilation modified from -10 -5 0 5 10 Halverson (2003: in prep.)

Figure by MIT OCW. Carbon Reservoirs, Fluxes and Residence Times

Species Amount Residence Time (yr)* δ 13 C 18 (in units of 10 gC) %o PDB** Sedimentary carbonate-C 62400 342000000 ∼ 0

Sedimentary organic-C 15600 342000000 ∼ -24

Oceanic inorganic-C 42 385 ∼ +0.46

Necrotic-C 4.0 20-40 ∼ -27

Atmospheric-CO2 0.72 4 ∼ -7.5

Living terrestrial biomass 0.56 16 ∼ -27

Living marine biomass 0.007 0.1 ∼ -22 Nemotodes most abundant Summary of Animal Phylogeny animals Ecdysomes- most diversity Individual body plans

Protostomes Bilateral symmetry, Organs

Tissues Deuterostomes

Animal multicellularity more compl. jelly tissues, not organs Radial symmetry 2layers with jelly Monophyletic= ‘sister’ to everything single common ancestor fungi ‘animal protist’ single cell 0 40 80 489.0 + _ 1.0 Ma 490 491.0 + _ 1.0 Ma Temporal Late 500 Orders Constraints for Middle Burgess shale fauna 510 510.0 + _ 1.0 Ma Neoproterozoic- Botomian 522.0 + _ 1.0 Ma Classes

520 Cambrian Atdabanian First Cambrian history trilobites Tommotian Early 530 531.0 + _ 1.0 Ma Nemakit- Treptichnus pedum 540 Daldynian -542.0 543.0 _ 1.0 Ma + Ma Namacalathus Shelly fossils ? and Cloudina 550 Is the base of the 555.0 + _ 0.3 Ma Kimberella 560 565.0 + _ 3.0 Ma Cambrian an

570 Doushantuo Fm. embryos (570 Ma?) 575.4 + _ 0.4 Ma Assemblage Ediacaran extinction event?? Neoproterozoic III

Millions of Years Before Present Years Millions of _ 580 580.7 + 0.7 Ma Gaskiers glaciation

590

600

610 Cryogenian

620 -5 0 5

Figure by MIT OCW. Namacalathus: more skeletal diversity in terminal Proterozoic reefs.

Image removed due to copyright restrictions. Please see Fig. 8a in Grotzinger, John P., et al. “Calcified Metazoans in Thrombolite- Stromatolite of the Terminal Proterozoic Nama Group, Namibia.” Paleobiology 26 (September 2000): 334-359. Models of Namacalathus morphology, based on serial sections through rocks. Living scyphopolyps Image removed due to copyright restrictions. (cnidarians) for comparison. Please see Fig. 10 in Grotzinger, John P., et al. “Calcified Metazoans in Thrombolite- Stromatolite Reefs of the Terminal Proterozoic Nama Group, Namibia.” Paleobiology 26 (September 2000): 334-359. Precambrian-Cambrian Boundary Extinction ?

Image removed due to copyright restrictions. Please see Fig. 5 in Knoll, Andrew H., et al. “Early Animal Evolution: Emerging Views from Comparative Biology and Geology.” Science 284 (June 25, 1999): 2129-2137. Image removed due to copyright restrictions. Please see Fig. 4.1-1 in Global Biodiversity Assessment. Dowdeswell, Elizabeth, and Heywood, Vernon H., ed. Cambridge, England: Cambridge University Press, 1996. ISBN: 0521564816. Permo-Triassic Boundary zWhere is it and how is it defined?

z Marine extinctions observed worldwide in the Upper Permian (Changhsingian)

z Base Triassic (Griesbachian) defined at the Global Stratotype, Section and Point , Meishan, China at the first appearance of a specific marine taxon, the conodont Hindeodus parvus

zFloral extinction: well defined ‘coal gap’ in terrestrial sediments worldwide

z eg demise of Glossopteris flora in Australia

z No precisely agreed way to correlate marine and terrestrial sections and an absence of sufficiently accurate geochronology z Terrestrial faunal extinction (eg Ward et al, Science 2005) Image removed due to copyright restrictions. Please see Fig. 3 in Hongfu, Yin, et al. “The Global Stratotype Section and Point (GSSP) of the Permian-Triassic Boundary.” Episodes 24 (June 2001): 102-114. http://www.stratigraphy.org/logpt.htm

Main extinction horizon in ash bed (Bed 25) Composite δ13C & Diversity Profiles

Image removed due to copyright restrictions.

Please see Fig. 3 in Payne, Jonathan L., et al. “Large Perturbations of the Carbon Cycle During Recovery from the End-Permian Extinction.” Science 305 (July 23, 2004): 506-509. Characteristics of Permian-Triassic Event

• Global regression of sea level; aggregation of supercontinent of Pangea; rarity of continuous sedimentation • Massive volcanism and emplacement of Large Igneous Provinces (LIPS) – 400 to 3700m thick basalts over ca 5 Ma • Uneven marine extinction; sessile animals worst hit and a terrestrial extinction as well • Immediate radiation of different physiological groups (disaster species??) than before and then stabilization of the classic Mesozoic fauna and flora. • More complex and sophisticated ecosystems; new insects like today’s and evidence of metabolic versatility eg Claraia which apparently could survive low pO2. Frequently used decay schemes; half-lives vary by a factor of > 100

238U Æ 206Pb 4.5 x 109 235U Æ 207Pb 0.71 x 109 40K Æ 40Ar 1.25 x 109 87Rb Æ 87Sr 47 x 109 147Sm Æ 144Nd 106 x 109 Courtesy of USGS. http://volcano.und.nodak.edu/vwdocs/volc_ images/north_aZircons:merica/washington.html Nature’s Acasta:Time Worlds Capsules oldest rock: (Ages in My)

Images removed due to copyright restrictions. No dates, no rates!!

Sam Bowring after Paul Hoffman

Images and text removed due to copyright restrictions.

Please see Abstract, Fig. 1 and 2 in Bowring, S. A., et al. “U/Pb Zircon Geochronology and Tempo of the End-Permian Mass Extinction.” Science 280 (May 15, 1998): 1039-1045.

NB Tempo of 13C excursion excludes mechanisms related to the long-term burial or erosion of sedimentary carbon Boundary Clay Bed 25 251-4 Ma (Bowring et al, 1998) Zone of volcanic microspherules

Image and text removed due to copyright restrictions.

Please see Fig. 4 and the final paragraph in Jin, Y. G., et al. “Pattern of Marine Mass Extinction near the Permian-Triassic Boundary in South China.” Science 289 (July 21, 2000): 432-436. Image and text removed due to copyright restrictions.

Please see Abstract and Fig. 1 in Mundil, Roland, et al. “Age and Timing of the Permian Mass Extinctions: U/Pb Dating of Closed-System Zircons.” Science 305 Combined chemical and heat (September 14, 2004): 1760-1763. treatment

Compensates for lead loss

Gives older ages and smaller ‘error’ ellipses Image and text removed due to copyright restrictions.

Please see Abstract and Fig. 3 in Mundil, Roland, et al. “Age and Timing of the Permian Mass Extinctions: U/Pb Dating of Closed-System Zircons.” Science 305 (September 14, 2004): 1760-1763.

Older ages better match the age of Siberian Traps massive volcanism ie death by association!! Siberian Traps 251- to 252 Ma

Bowring et al (1998) Mundil et al (2001) 38 38

36 250.2 ± 0.2 36 253.5 ± 0.4 34 250.4 ± 0.5 34

Lower Triassic 30 30 250.7 ± 0.3 252.5 ± 0.3 251.4 0.3 ± > 254

22 22

19 252.3 ± 0.3 19

16 16 15 15 252.0 ± 0.4 Permain

13 13

Changhsingian Stage 12 12

9 9 253.4 ± 0.2 257.3 ± 0.7?

1 1 Figure by MIT OCW. A simplified stratigraphic column from the Permo-Triassic section at Meishan China showing bed-by-bed comparison of dated ash-beds as reported by Bowring et al. (1998) and Mundil et al. (2001). Image removed due to copyright restrictions.

Please see Fig. 1 in Jin, Y. G., et al. “Pattern of Marine Mass Extinction near the Permian- Triassic Boundary in South China.” Science 289 (July 21, 2000): 432-436. Image removed due to copyright restrictions.

Please see Fig. 2 in Jin, Y. G., et al. “Pattern of Marine Mass Extinction near the Permian- Triassic Boundary in South China.” Science 289 (July 21, 2000): 432-436. PTB Definition Problems

• Age assignments weak in absence of ash beds (most known sections worldwide except south China) • Biostratigraphic age assignments in absence of index fossils are problematic (Parochial vs Cosmopolitan taxa) • Uncertainties in correlating marine and terrestrial sedimentary sections because fauan/flora don’t overlap • Multiple isotopic excursions in δa and δo, rare to have both • Uncertainties in the tempo and ‘causes’ of carbon isotopic excursions Isotopic pattern of P/T contact in Woodada-2 Perth Basin Image removed due to copyright restrictions. Please see Fig. 1 in Foster, C. B., et al. “The An ‘excursion’ or Permian-Triassic Boundary in Australia – Organic Carbon Isotopic Anomalies Related to Organofacies, not a Biogeochemical something else ‘Event’.” In Ninth Annual V. M. Goldschmidt Conference, Abstract #7301.

http://gs.wustl.edu/archives/goldschmidt/1999 /ABSTRCTS/1-400/7301.pdf first appearance of Claraia sp. Woodada-2 8 6 4 ε =δcarb-δkerg ~28.5‰ 2 (Hayes et al., 1989) 0 -2

C carbonate -4 13

δ -6 -8 -32-30-28-26-24-22-20 δ13C kerogen 13 TOC (%) δ C (%o) 0 12 -33 org -21 Formation Isotopics of 3300

P/T contact 3400 FORMATION TRIASSIC MT. GOODWIN

TERN CUTTINGS in Bonaparte 3500 SANDSTONE Palynology ) (Zones) H4 m (

t PP5.5-PP6 p

Basin e D 3600 PP6 PP5.4-PP6 CORES 1-9 PP5.4 abundant spinose 3700

CAPE HAY PERMIAN MEMBER acritarchs HYLAND BAY FORMATION

PP4.3.2- CUTTINGS 3800 PP5 CORE 10 PP4.3.2 CUTTINGS

93.5 % Spinose acritarchs

LITHOLOGY

Sandy shale

Shale / claystone

Sandstone

Limestone

Interbedded shale & sandstone

Isotope data of Figure by MIT OCW. Morante 1995 Tern-3

δ13C kerogen -34-32-30-28-26-24-22-20 2380 2400 2420 2440 2460

Depth (m) 2480 2500 2520 0 20 40 60 80 100 %Wood Debris PTB Killing Mechanisms

#1 Overturn of an anoxic ocean; CO2 and H2S poisoning

#2 Explosive volcanism and associated icehouse/greenhouse followed by productivity collapse (numerous authors)

#3 Regression, catastrophic methane release and associated greenhouse (numerous authors)

#4 Impact (Becker and Poreda) PTB Killing Mechanisms #1 Overturn of an anoxic ocean

Text removed due to copyright restriction.

Please see Abstract in Knoll, A. H., et al. “Comparative Earth History and Late Permian Mass Extinction.” Science 273 (July 26, 1996): 452-457. PTB Killing Mechanisms #1 Overturn of an anoxic ocean

Image removed due to copyright restriction.

Please see Fig. 2 in Isokazi, Yukio. “Permo-Triassic Boundary Superanoxia and Stratified Superocean: Records from Lost Deep Sea.” Science 276 (April 11, 1997): 235-238. PTB Killing Mechanisms #1 Overturn of an anoxic ocean (Holser et al., 1980’s; Kajiwara Paleo-cubed , 1994; Wignall and Twitchett, Science1996; Knoll, Bambach, Canfield and Grotzinger Science 273, 455 (1996); Isozaki, Y. Permo-Triassic Boundary Superanoxia and Stratified Superocean: Records from Lost Deep Sea. Science 276: 235-238 (1997 )

++ Sulfur & carbon isotope anomalies, extensive deposition of pyrite (Fe and H2S)

Analogies to Neoproterozoic glacial times – rapid 13C changes, carbonate crystal fans etc

Selective susceptibility of animals with no gills, weak internal circulation and low metabolic rates Sessile animals such as corals, bryozoans, crinoids and echinoderms

Selective survival and rapid recovery of animals with gills, active circulation, and high metabolic rates Motile taxa such as Arthropods, Cephalopods (Ammonoids, Nautiloids), Conodont animals, bivalves PTB Killing Mechanisms

#1 Overturn of an anoxic ocean

Text removed due to copyright restriction.

Please see Preface in Rabalais, Nancy N., and Turner, R. Eugene, eds. Coastal Hypoxia: Consequences for Living Resources and Ecosystems. No. 58, Coastal and Estuarine Studies Series. Washington, DC: American Geophysical Union, 2001. PTB Killing Mechanisms #1 Overturn of an anoxic ocean NEED TO KNOW: FACT vs. FICTION The dead zone, also known as Gulf hypoxia, has doubled in size since researchers first mapped it in 1985. Despite this trend, last year's swath of oxygen-depleted bottom waters spanned a mere 4,400 square kilometers--only about one fifth of the record size in 1999. Because nitrogen inputs to the Mississippi River Basin have stayed constant, some people have falsely assumed that nitrogen must not cause hypoxia. In reality, factors other than nitrogen can cause the size of the dead zone to fluctuate. Midwestern floods in 1999 washed more nutrients down the Mississippi, for instance, and severe drought caused river levels to drop in 2000. Strong winds over the Gulf of Mexico can also resuscitate salty bottom waters by mixing them with the oxygen-rich river water that usually floats above.

Courtesy NOAA PTB Killing Mechanisms

#1 Overturn of an anoxic ocean

Text removed due to copyright restriction.

Please see Graham, Sarah. “Persistent Toxic Gas Eruptions Plague Waters off Namibian Coast.” Scientific American News, February 1, 2002.

http://www.sciam.com/article.cfm?articleID=000054EE-E172-1CCE-B4A8809EC588EEDF PTB Killing Mechanisms #1 Overturn of an anoxic ocean

Image removed due to copyright restriction.

Please see Fig. 1 in Weeks, Scarla J., et al. “Massive emissions of toxic gas in the Atlantic.” Nature 415 (January 31, 2002): 493-494. PTB Killing Mechanisms

#1 Overturn of an anoxic, CO2-rich ocean, hypercapnia and H2S poisoning (Numerous papers prior to 1996; effectively articulated by Knoll, Bambach, Canfield and Grotzinger, Science 1996).

#2 Explosive volcanism and associated icehouse/greenhouse followed by productivity collapse(numerous authors)

#3 Regression, methane release and associated greenhouse (numerous authors)

#4 Impact (Becker et al., Science 291, 1530) PTB Killing Mechanisms #2 Extensive, incl. explosive volcanism and associated icehouse/greenhouse (numerous authors) Huge abundances of volcanic spherules in the China PTB sections Siberian Traps and S. Chinese volcanism but these appear to be long-term events with only partial overlap (see Erwin Sci Am) More recent instances of massive volcanism had little obvious effect on biodiversity PTB Killing Mechanisms #3 Regression, methane release and associated greenhouse (numerous authors)

Paucity of Late Permian and E. Triassic sediments and continuous sedimentation rapid 13C and repeated excursions

Loss of habitat for sessile animals such as corals, bryozoans, crinoids and echinoderms

Selective survival of mobile animals such as Arthropods, Cephalopods (Ammonoids, Nautiloids), conodont animals, bivalves (Knoll et al; Jin et al) Methane on Earth

Courtesy USGS http://woodshole.er.usgs.gov/project-pages/hydrates/what.html Methane

Courtesy USGS http://woodshole.er.usgs.gov/project-pages/hydrates/what.html http://geology.usgs.gov/connections/images/mms_images/laminae.jpg

Hydrate seams in mud

Hydrate outcropping on seafloor and colonised by chemosynthetic ecosystem

Courtesy USGS http://geology.usgs.gov/connections/images/mms_images/seafloor_mounds.jpg Courtesy USGS http://woodshole.er.usgs.gov/project-pages/hydrates/ Methane

Courtesy USGS http://woodshole.er.usgs.gov/project-pages/hydrates/what.html Methane

Courtesy USGS http://woodshole.er.usgs.gov/project-pages/hydrates/where.html Methane

Courtesy USGS http://pubs.usgs.gov/fs/gas-hydrates/figures/fig3.html Methane – Cascadia Margin

Courtesy DOE http://www.netl.doe.gov/technologies/oil-gas/FutureSupply/MethaneHydrates/about-hydrates/cascadia-margin.htm PTB Killing Mechanisms #4 Impact (Becker and Poreda)

Image removed due to copyright restriction.

Please see Fig. 1 in Becker, Luann, et al. “Impact Event at the Permian-Triassic Boundary: Evidence from Extraterrestrial Noble Gases in Fullerenes.” Science 291 (February 23, 2001): 1530-1533. Images and text removed due to copyright restrictions. Please see the Wikipedia article on Buckminsterfullerene, http://en.wikipedia.org/wiki/Buckminsterfullerene#Buckmi nsterfullerene. 3He as a tracer

Extraterrestrial 3He is the major source – From solar wind and implanted in bolides and IDP – 3He/ 4He = 100 (ET) Ra vs 0.03 Ra (Terrestrial He) normalized to atm. value of 1.39 x 10-6 – Vaporized from bolides and large IDP by heat on entry – Retained in small IDP and normally accrete uniformly – Can give estimated of sedimentation rate independent of absolute time – Enhanced accretion during ‘dusty’ episodes such as comet showers – All He leaks so not useful over >400Ma timescales PTB Killing Mechanisms #4 No 3He evidence for impact (K. A. Farley and S. Mukhopadhyay, Science 293, 2343a, 2001)

Image removed due to copyright restriction.

Please see Fig. 1 in Farley, K. A., et al. “An Extraterrestrial Impact at the Permian- Triassic Boundary?” Science 293 (September 28, 2001): 2343a. Because the "3He- enriched" sample PTB Killing Mechanisms from Sasayama is significantly older than Meishan Bed #4 Impact (Becker and Poreda) ?? 25, they cannot have been from the same impact event. Yukio Isozaki

In other words, in Japan, this bed is Image removed due to copyright restriction. Permian Please see Fig. 2 in Becker, Luann, et al. “Impact Event at the Permian-Triassic Boundary: Evidence from Extraterrestrial Noble Gases in Fullerenes.” Science 291 (February 23, 2001): 1530-1533. Image and text removed due to copyright restriction.

Please see Abstract and Fig. 1 in Becker, L., et al. “Bedout: a Possible End-Permian Impact Crater Offshore of Northwestern Australia.” Science 304 (June 4, 2004): 1469-1476. Images removed due to copyright restriction.

Please see Fig. 2 and 3 in Becker, L., et al. “Bedout: a Possible End-Permian Impact Crater Offshore of Northwestern Australia.” Science 304 (June 4, 2004): 1469-1476. Images removed due to copyright restriction.

Please see Fig. 6 and 11 in Becker, L., et al. “Bedout: a Possible End-Permian Impact Crater Offshore of Northwestern Australia.” Science 304 (June 4, 2004): 1469-1476. Text removed due to copyright restriction.

Please see Wignall, Paul, et al. “Is Bedout an Impact Crater? Take 1.” Science 306 (October 22, 2004): 609-610. and Renne, Paul R., et al. “Is Bedout an Impact Crater? Take 2.” Science 306 (October 22, 2004): 610-612. Biogeochemical Carbon Cycle in Modern Ocean hν

CO2 + H2O Æ CH2O + O2 Photosynthesis Å Respiration

2- + H2S + 2CO2 + 2H2O Å CH3COOH + SO4 +2H Sulfate Reduction sediment Links Between Carbon and Sulfur Cycles hν

CO2 + H2O Æ CH2O + O2 Photosynthesis Å Respiration

2- + H2S + 2CO2 + 2H2O Å CH3COOH + SO4 +2H Sulfate Reduction

sediment Carbon Cycle in a Stratified Ocean hν

CO2 + H2O Æ CH2O + O2 Photosynthesis

2- + H2S + 2CO2 + 2H2O Å CH3COOH + SO4 +2H Sulfate Reduction

Euxinic Water Column

sediment Green sulfur bacteria hν Chlorobiaceae

Anoxygenic photosynthesis

H S + CO Biomarkers2 of Chlorobiaceae2 O2 Green-pigmented hν Chlorobiaceae chlorobactane H S 20 m 2 Brown-pigmented SO 2- + C Chlorobiaceae 4 org isorenieratane 100 m ● requires reduced sulfur

● requires light sediment ● strictly anaerobic Summons et al., 1987 Molecular Markers for Chlorobiaceae

Biolipid precursor C40 carotenoid

free isorenieretene (found in Chlorobiumsp.) H2S / H2 cyclisation/ S aromatisation S

S C-C bond covalently-bound (partially reduced) cleavage isorenieretene H S / H 2 2 free and bound covalently-bound isorenieratane(fully reduced) complex polyaromatichydrocarbons m/z = 133/134 S-S and C-S linkage cleavage m/z = 133/134

C-C bond cleavage *C40 isorenieratane *C14-30 aryl isoprenoids (preserved extractable HC) (preserved extractable HCs)

- Damsté, De Leeuw et al., 1990-1995 Meishan Stratigraphy & Radiometeric Ages 30 samples from beds 22 to 39 (ca. 3 Ma) Bed Lithological (PDB) No. Column -1-2 0 1 2 3 4 5 249.5 (Ma) molecular lipid biomarkers 34-36 250 13 15 bulk geochemical parameters (TOC, δ Corg, δ Norg)

33 29-32 250.5 28 Meishan-1 core 27 251 drilled Jan 2004 26 25 251.5

23-24

252

22 21 20 17 252.5 15 12-14 11 253 9 8 7 253.5

1- 6

Figure by MIT OCW. Multiple radiometric ages help constrain pace Ash in bed 25 = 251.4 ± 0.3 Ma, Bowring et al, 1998) 252.6 ± 0.2 Ma Mundil et al, 2004 depth metres 1995 1990 1985 1980 1975 1970 1965 Isorenieratane Biogeochemical Proxies atHovea-3PerthBasin 04 p TOC ppm A) 20 0 Aryl isoprenoids 0 p TOC ppm B) 45 C C C C 19 20 18 90 90 05 p x1000 ppm Porphyrins 2.5 C) V=O Ni (Fe 00.40.8 D +Fe D) p )/Fe T 60 -6 δ 34 ‰ 40 -4 E) S pyrite 20 -2 36 -3 δ 31 -3 F) 13 ‰ Pristane Phytane C 26 -2 Claraia size (mm) size Claraia 0 mm G) 50

100

Upper Permian Permian Upper Upper Lower Triassic Triassic Lower Lower

Changhsingian Changhsingian

Griesbachian Griesbachian Abundance of GSB Biomarkers Meishan-1 core

012-32 -28 -24 0123456 0246810 0246 85

90 bed 37 bed 37

95 bed 35

C18 C19

C20

Depth (m) 100

bed 30

105 bed 26 bed 27 bed 25 bed 24 bed 24 110

115

TOC (wt%) δ13C kerogen (‰VPDB) Pristane/Phytane Aryl isoprenoids (ppm TOC) Isorenieratane (ppm TOC) Paleographic Reconstruction: Ron Blakey, Northern Arizona University

Courtesy Ron Blakey. Used with permission. http://jan.ucc.nau.edu/rcb7/presentmoll.jpg 50 Ka

Courtesy Ron Blakey. Used with permission. http://jan.ucc.nau.edu/ 20 Ma

Courtesy Ron Blakey. Used with permission. http://jan.ucc.nau.edu/ 35 Ma

Courtesy Ron Blakey. Used with permission. http://jan.ucc.nau.edu/ 50 Ma

Courtesy Ron Blakey. Used with permission. http://jan.ucc.nau.edu/ 65 Ma

Courtesy Ron Blakey. Used with permission. http://jan.ucc.nau.edu/ 90 Ma

Courtesy Ron Blakey. Used with permission. http://jan.ucc.nau.edu/ 105 Ma

Courtesy Ron Blakey. Used with permission. http://jan.ucc.nau.edu/ 120 Ma

Courtesy Ron Blakey. Used with permission. http://jan.ucc.nau.edu/ 150 Ma

Courtesy Ron Blakey. Used with permission. http://jan.ucc.nau.edu/ 170 Ma

Courtesy Ron Blakey. Used with permission. http://jan.ucc.nau.edu/ 200 Ma

Courtesy Ron Blakey. Used with permission. http://jan.ucc.nau.edu/ 220 Ma

Courtesy Ron Blakey. Used with permission. http://jan.ucc.nau.edu/ 240 Ma

Courtesy Ron Blakey. Used with permission. http://jan.ucc.nau.edu/ 260 Ma

Courtesy Ron Blakey. Used with permission. http://jan.ucc.nau.edu/ Meishan Section

Image removed due to copyright restrictions. Please see http://www.scotese.com/images/255.jpg

Meishan sediments deposited on N.-E. margin of Paleotethys equatorial latitudes, deepwater shales Meishan (Core 1) Bulk geochemical parameters

-85 -85 -85 0246 0 0.5 1.0 1.5 -34 -32 -30 -28 -26 -24 -22

-90 -90 -90 37-2 37-2 37-2

-95 -95 -95 dysoxic

-100 -100 -100 depth/m depth/m depth/m

34-1 34-1 34-1 32-3 -105 -105 -105 26-3 26-3 29-1 26-3 24-6 24-6 24-6 23-4 23-4 -110 23-4 -110 -110 22-3 22-3 22-3 anoxic

-115 -115 -115 TOC/wt% δ13Corg ( kerogen) Pristane/Phytane Identification of Isorenieratane at the PTB

Images removed due to copyright restriction. sample Please see Fig. 1a in Grice, Kliti, et al. “Photic Zone Euxinia during the Permian-Triassic Superanoxic Event.” Science 307 (February 4, 2005): 706-709. and Fig. S2 in the associated Online Supplement.

standard

Isorenieratane indicative of ‘brown pigmented’

Green Sulfur Bacteria Æ

H2S 20 -100m from surface Abundance of GSB Biomarkers Meishan-1 core euxinia repeatedly in Triassic

012-32 -28 -24 0123456 0246810 0246 85

90 bed 37 bed 37

95 bed 35

C18 C19

C20

Depth (m) 100

bed 30

105 bed 26 bed 27 bed 25 bed 24 bed 24 110

115

TOC (wt%) δ13C kerogen (‰VPDB) Pristane/Phytane Aryl isoprenoids (ppm TOC) Isorenieratane (ppm TOC)

Intense euxinia in Late Permian Bed 24 δ15N of Meishan Organic Matter

-ve +ve -85 -4 -2 0 2 4 z Positive values (+3 to +2) in late Permian Beds 22-24 -90 37-2 15 36-3 z Trend to zero or negative values of δ N in latest Permian reflects depletion of 35-1 35-2 -95 nitrate/nitrite pool driven by euxinic cond.

34-12 zLarge swings in E. Triassic may reflect -100 waxing and waning of euxinia depth/m 34-3 34-1 z Predominantly cyanobacterial primary -105 30-1 production 26-2 b24 Peaks in 2-MeHI >15% 23-4 -110 22-3 Peaks of aryl isoprenoid

-115 abundance δ15N kerogen Hopane/Sterane and Methylhopane ratios for Meishan Core

1 10 100 1000 010203040 60 80 100 -85 -85 -85

39-1 39-1

-90 -90 -90 37-2 37-2 36-3 36-3 36-3

-95 -95 -95

34-12 34-12 34-12

-100 -100 -100 depth/m depth/m 34-1 34-1 34-1 -105 -105 -105 30-1 26-3 26-3 24-6 24-2 24-2 -110 -110 -110 22-3 22-3 22-3

-115 -115 -115 hopane/sterane % 2Me/(2Me + des) %(2/2+3) Me hopane

Hop/st> 100 in beds 35/36 Extremely high cyanobacterial input (max. 190!) In top of bed 34-bed 36 Central Tethys Ocean m/z = 134 36.54 Section Twitchett 39.09 ‘D’ Section Outcrop 41.78 Present-day Tibet

36.54 39.09 Aryl isoprenoids 41.78

36.54 39.07 41.78

Image removed due to copyright restrictions. 36.54 Please see http://www.scotese.com/images/255.jpg 33.28 31.43 39.09

41.78 28.92 45.20

19 18 33.26 20 36.54 21 16 39.07 17 41.78 28.40 25.51 45.48 48.71

http://www.scotese.com 5.00 30.00 35.00 40.00 45.00 50 Great Bank of Guizhou

Image removed due to copyright restrictions.

Please see Fig. 1 in Payne, Jonathan L., et al. “Large Perturbations of the Carbon Cycle During Recovery from the End-Permian Extinction.” Science 305 (July 23, 2004): 506-509.

Meishan 18 20 15 19 16

14 21

17 Image removed due to copyright restrictions.

Please see http://www.scotese.com/images/255.jpg PGD 84 ~ 250 Ma

PGD-104 ~ 251 Ma http://www.scotese.com

12.00 16.00 20.00 24.00 28.00 Aryl isoprenoids m/z 134 Peace River Embayment Image removed due to copyright restrictions.

Triassic rocks to east of dashed line Please see a map of the Peace River Embayment, http://www.ags.gov.ab.ca/publications/ATLAS_WWW/ are in the subsurface. A_CH15/FG15_14.shtml

Calais, Crooked Creek + other cores ~ 25 km apart

Image removed due to copyright restrictions. Please see http://www.scotese.com/images/255.jpg

http://www.scotese.com SYSTEM STAGE BIOZONE FORMATION APPLIED timorensis Doig Fm. STRATIGRAPHY ANISIAN RESEARCH GROUP regale MIDDLE LOWER

jubata

SPATHIAN triangularis Toad Fm. homeri collinsoni milleri SMITHIAN waageni

pakistanensis Pachycladina Triassic Montney Fm. Sulphur Mt. Fm.

Lower cristagalli DIENERIAN Kummeli

isarcica Ellisonia GRIESBAC-

Grayling Fm. Hindeodus parvus from subsurface

planata parvus-

HIAN carinata- taylorae Montney Fm., Western Canada shenimeishanensis CHANGHSIN- GIAN Calais and Cr. Ck samples are from

rosenkrantzi condensed ?? parvus Zone and younger WUCHIAPIN- basal Sulphur -postbitteri Mountain GIAN Fm. ??

Upper Mowitch Permian CAPITANIAN Belloy

bitteri or Ranger Canyon WORDIAN or Fantasque Fm.

Figure by MIT OCW.

Modified from Henderson, 1997. Aryl isoprenoids present in 7 samples from 4 wells at the H. parvus level

100 15 16 ABR016 18 Chevron Crooked Creek 3500ft Aromatic hydrocarbons

RI m/z 134.00 20 14 19 isorenieratane

21 17 β- isorenieratane

20.00 40.00 60.00 80.00 100.00 Kap Stosch Late Permian to Early Triassic rocks from outcrop Curt Teichert, and Bernhard Kummel Bulletin of Canadian Petroleum Geology; December 1972; v. 20; no. 4; p. 659-67 Permian-Triassic boundary in the Kap Stosch area, east Greenland Kap Stosch

Image removed due to copyright restrictions. Please see http://www.scotese.com/images/255.jpg

http://www.scotese.com SIM m/z = 134.1 Barney Ck. Fm aromatic hydrocarbon fraction Æ retention standard for 2,3,6-trimethylaryl isoprenoids 16 18

19 isorenieratane 22 20 21

18 SIM m/z = 134.1 19 C# of aryl isoprenoid 19990456 aromatic hydrocarbon fraction Greenland, Kap Stosch

20 Upper Permian; loc 13.75 16 21 22 isorenieratane

SIM m/z = 134.1 19 18 19990445 aromatic hydrocarbon fraction 20 Greenland, Kap Stosch Lower Triassic; loc 1

16 21 isorenieratane

20 40 60 80 100

Time min. Hydrogen sulfide poisoning?

Grice et al. Science, 2005 z Spread of anoxic and sulfidic waters onto continental shelves

Kump, Pavlov and Arthur, Geology 33 (May) 2005

z Flux of H2S to the atmosphere that depletes hydroxyl radicals in the troposphere z H2S plume would be persistent; could poison terrestrial biota PTB Summary Characteristics

z Extinction selectively killed sessile organisms with calcareous skeletons; vertebrates less affected

z Recovery was very protracted > 10 million years

z Biomarker and isotopic evidence for deep ocean euxnia across P-T 13 13 15 34 z Multiple excursions in δ Ccarb , δ Corg, δ Norg, δ Spyrite near boundary

z These anomalies indicate there were major, long-term changes in the redox state of the ocean and a long-term disruption of the C-cycle

z Evidence for near-surface euxinia at PTB from 5 localities Æ Tethys and Panthalassic were euxinic Æ compelling extinction mechanism PTB Summary

H2S in ocean & atmosphere toxic to all but bacterial life What are the underlying causes of this oceanic euxinia? z The ‘complex web of causality’ z Aggregation of Pangea in greenhouse worldÆ low equator-pole temperature differentialÆ sluggish ocean circulation z Massive weathering of Paleozoic coals Æ drawdown of pO2 and rise of pCO2; OM for SRB z Long delay in recovery until ocean is re-ventilated z Environmental disturbance may have been made more extreme due to intense volcanism Loci of Aryl Isoprenoid Occurrences

Kap Stosch Meishan mid N. lat., paralic shales N.-E. margin Paleotethys equatorial, deepwater shale & carb. Peace River Embayment mid N. lat., Panthalassa, paralic shales Great Bank of Guizhou Image removed due to copyright restrictions. E. margin of Paleotethys Please see http://www.scotese.com/images/255.jpg equatorial, carbonates

Tibet S. lat., Tethys carbonates

Perth Basin High S. lat. Tethys, paralic shales http://www.scotese.com Carbon Cycle Dynamics (Berner RA, PNAS, 99, 4172 2002)

Image removed due to copyright restrictions. Please see Fig. 2 in Bowring, S. A., et al. "U/Pb Zircon Geochronology and Tempo of the End-Permian Mass Extinction." Science 280 (1998): 1039-1045. Carbon Cycle Dynamics

Structure of GeoCarb Model of sources and sinks of carbon

Fig. 2. Diagram for the carbon cycle box model used in the present paper. Fv flux of volcanic CO2; Fm flux of methane from methane hydrates (the methane is assumed to be oxidized to CO2 essentially instantaneously); Fwc uptake of CO2 by means of the weathering of carbonates (twice this value is the flux of carbon to the oceans from carbonate weathering); Fwsi uptake of atmospheric CO2 by means of the weathering of Ca–Mg silicates with transfer of the carbon to the oceans; Fbg burial flux of organic carbon in sediments; Fwg weathering flux of ancient sedimentary organic carbon (kerogen); Fbio flux of CO2 caised by the mass mortality of terrestrial biota; Fbc burial flux of marine carbonates ( flux of CO2 from ocean to the atmosphere). Modified from Beerling and Berner (18).

Methane hydrate collapse and oxidation at realistic rates, with

oxidation to CO2 on realistic timescales can explain observed large carbon isotopic shifts.

However, resultant pCO2 increase is not as high as seen through most of Mesozoic so cannot have killed by

hypercapnia (CO2 poisoning).

Fig. 3. Plots of oceanic 13C and atmospheric CO2 vs. time as a result of the input of methane hydrate-derived CH4 to the atmosphere or oceans. It is assumed that the methane is oxidized essentially instantaneously to CO2 in either case. (A) 13C. (B) CO2.

Volcanism and CO2 release at realistic timescales cannot explain observed carbon isotopic shifts.

May have been a contributory factor

Fig. 4. Plots of oceanic 13C and atmospheric CO2 vs. time as a result of the input of volcanically derived CO2. The terms fast and slow refer to inputs lasting approximately 30,000 and 200,000 years, respectively. (A) 13C. (B) CO2.

Fig. 5. Plots of 13C and atmospheric CO2 vs. time Fig. 6. Plots of oceanic 13C and atmospheric CO2 for the sudden mass mortality of terrestrial vs. time as a result of a sudden drop in global vegetation with all vegetation plus soil carbon organic C burial rate from 60 Gt C/kyr to 24 Gt converted to CO2. Note the much shorter time C/kyr with a constantly maintained organic C scale compared with Figs. 3 and 4. weathering rate of 60 Gt C/kyr.

Alone, mass mortality, productivity collapse, OM remineralization, CO2 release and cessation of biological pump at realistic timescales cannot

explain observed carbon isotopic shifts or generate toxic amounts of CO2. Cannot have been the sole cause but may have been a contributory factor

Fig. 9. Plots of 13C and CO2 vs time for the combined inputs of carbon to the atmosphere from mass terrestrial mortality, CH4 hydrate decomposition, and volcanic CO2 degassing combined with an imbalance in the rates of burial and weathering of sedimentary organic matter.

A combination of productivity collapse, imbalance between burial and weathering,

CH4 release and volcanic degassing at realistic timescales can explain observed carbon isotopic shifts and amounts of CO2 sufficient to create intense greenhouse.

Fig. 1, 2, 3, 4, 5, 6, and 9 from Berner, Robert A. "Examination of Hypotheses for the Permo-Triassic Boundary Extinction by Carbon Cycle Modeling." PNAS 99 (April 2, 2002): 4172-4177. Copyright 2002 National Academy of Sciences, USA. PTB Killing Mechanisms #5 Tangled web of causality Erwin, Nature 367, 231 (1994); Berner PNAS 99, 4172 (2002) Regression = loss of habitat

Exposure of supercontinent (Pangea) exacerbates loss of habitat

Large supercontinent and its paleogeography = a deep ocean that might more easily become anoxic

Volcanism, XS CO2, warming, productivity collapse

However, cannot sustain exceedingly high CO2 in presence of limestone on ocean floor because this dissolves with a buffering effect

Rapid E. Triassic transgression destroyed coastal habitat and contributed to floral extinctions Terrestrial primary productivity on the land replaced by primary productivity in ocean Æ reorganization of C-cycle (Berner) Composite δ13C & Diversity Profiles Payne et al. Science 305, 506 (2004)

Image removed due to copyright restrictions.

Please see Fig. 3 in Payne, Jonathan L., et al. “Large Perturbations of the Carbon Cycle During Recovery from the End-Permian Extinction.” Science 305 (July 23, 2004): 506-509.