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Oceanic LIPs: The Kiss of Death Oceanic plateaus have been drilled from the JOIDES Resolution drill ship. PHOTO ODP Andrew C. Kerr1 ceanic plateaus represent large areas (~1 × 106 km2) of thickened oceanic crust formed from rapidly erupted lava (<3 Myr). These plateaus have formed throughout most of geological time. They generally correlate with periods of environmental catastrophe characterised by oceanic anoxia, leading to black shale formation and mass extinction events. Such correlations are particularly evident in the Cretaceous and can be partly attributed to the release of CO2 during oceanic plateau formation, which ultimately resulted in a runaway greenhouse effect. Additionally, sea level rise and disruption of oceanic circulation patterns by displacement of seawater during plateau formation contributed to increased environmental stress and biotic extinction. O (93.5 Ma) and during the Aptian (124–112 Ma) (Sliter 1989; Bralower et al. 1993; Jahren 2002). This link appears to extend back to the Precambrian: Condie et al. (2001) have noted that significant black shale events occurred at ~1.9 and 2.7 Ga and that these correlate with the formation of mantle plume-derived large igneous provinces (LIPs) and warmer palaeoclimates. Thus, there seems to be a temporal association, throughout a significant proportion of geologKEYWORDS: mass extinction, oceanic plateau, ical time, between periods of black shale, anoxia, mantle plume global oceanic environmental crises and oceanic plateau formaINTRODUCTION tion. In the remainder of this contribution the possible Although the potentially devastating environmental causal links between oceanic plateaus and oceanic environimpact of continental flood basalts has been extensively mental change will be reviewed, with particular reference to discussed by many authors (Wignall 2001; articles by Self et Cretaceous events. al. and Wignall this issue), the global environmental effects of oceanic plateaus – the marine equivalent of continental OCEANIC PLATEAU VOLCANISM AND flood basalts – have received comparatively little attention. Oceanic plateaus represent over-thickened areas of oceanic crust (>10 km) in which the bulk of the >1 × 106 km3 lava volume appears to have erupted in less than 2–3 Myr. These plateaus generally cover an area in excess of 1 × 106 km2 and result from anomalously high rates of melt production in the mantle. These high melt-production rates are most likely due to the excess heat from a deep-rooted mantle plume (Campbell this issue). Oceanic plateaus are more buoyant than oceanic crust of normal thickness generated at a mid-ocean ridge. This buoyancy means that oceanic plateaus are more resistant to subduction, a feature which results in partial accretion onto continental margins. In this way oceanic plateaus can be preserved in the geological record and can be recognised back to the earliest Archaean. Periods of oceanic environmental crisis can be identified in the geological record by the occurrence of black shales, which are indicative of low-oxygen or oxygen-absent conditions in the deep ocean. Vogt (1989), Sinton and Duncan (1997), and Kerr (1998) have noted the coincidence of global oceanic anoxia, black shale deposition, mass extinction and oceanic plateau formation in the Cretaceous, particularly around the Cenomanian–Turonian boundary 1 School of Earth, Ocean and Planetary Sciences Cardiff University, Main Building Park Place, Cardiff, Wales CF10 3YE, UK E-mail: [email protected] ELEMENTS, VOL. 1, PP. 289–292 GLOBAL OCEANIC ANOXIA AT THE CENOMANIAN–TURONIAN BOUNDARY Oceanic Volcanism Arguably, the clearest link between oceanic plateau volcanism and environmental perturbation can be seen around the Cenomanian–Turonian (C–T) boundary. This time period is marked by the formation of the Caribbean– Colombian oceanic plateau (eastern Pacific) and parts of both the Kerguelen Plateau (Indian Ocean) and possibly the Ontong Java Plateau (western Pacific) (FIG. 1). Also around this time, India and Madagascar were beginning to rift apart, and this event was associated with volcanism at the Marion hotspot, which resulted in flood basalt eruptions on Madagascar and basaltic lavas offshore. Due to the continued breakup of Gondwana, the length of the global ridge system increased in the mid–late Cretaceous, resulting in a significantly greater volume of lava erupted globally at midocean ridges. Kerr (1998) has calculated that the peak production of oceanic crust (both intrusive and extrusive) around the C–T boundary was of the order of 45 × 106 km3, with ~10 × 106 km3 of this erupted on the seafloor (FIG. 2). Stratigraphic Characteristics The stratigraphic succession around the C–T boundary is characterised by black organic-rich shales, signifying anoxic oceanic conditions. This black shale event was associated with a second-order mass extinction event marked by the demise of 26% of genera (Sepkoski 1986). The C–T boundary is also characterised by a sharp increase in δ13C from 1.5 289 D ECEMBER 2005 Cenomanian–Turonian plate tectonic reconstruction showing the location of ~90–93 Ma and 123–110 Ma large igneous provinces. Cenomanian–Turonian boundary black shale deposits are also shown. The black shale localities are taken from Arthur et al. (1987), Herbin et al. (1987), Summerhayes (1987), and Yurtsever et al. (2003). FIGURE 1 to 4‰ in pelagic limestones, a decline in 87Sr/86Sr of seawater and evidence for a significant transgression (FIG. 2). Oxygen isotope evidence reveals that globally averaged surface temperatures at the C–T boundary were 6 to 14°C warmer than now (Kaiho 1994). This temperature rise was caused by elevated CO2 levels in the atmosphere. Modelling by Berner (1994) suggests atmospheric CO2 levels at this time were up to six times greater than pre-industrial levels and reached a peak around the C–T boundary. Links between Oceanic Plateau Volcanism and Environmental Catastrophe The coincidence of extensive oceanic plateau volcanism and the physical and chemical phenomena outlined above demand that we look for the causal links between oceanic plateau volcanism, global oceanic anoxia and warming, and mass extinction events. The formation of LIPs on both the continents and the oceans is often accompanied by lithospheric uplift and doming (Larson 1991; Nadin et al. 1997). Under the oceans, this elevation, in combination with the displacement of water due to the eruption of ~10 × 106 km3 of lava onto the ocean floor, results in a significant rise in sea level (FIG. 3). This mechanism may provide an explanation for at least part of the estimated ~100 m sea level rise which reached a maximum at the C–T boundary. The elevation of the sea floor, from both plume uplift and voluminous lava extrusion, during oceanic plateau formation could also have disrupted important oceanic circulation systems around the C–T boundary. The Caribbean–Colombian oceanic plateau formed close to the proto-Caribbean seaway between North and South America (FIG. 1). At this time, the only major source of deep, cold, oxygenated water for the juvenile Atlantic was the Pacific, and the water had to pass through this proto-Caribbean seaway. The formation of such a major volcanic edifice and the associated shallowing of seawater so close to this oceanic gateway would have restricted the flow of deep oxygenated water from the Pacific to the Atlantic and thus increased the extent of oceanic anoxia in the Atlantic (de Boer 1986). Although volcanism undoubtedly contributed to the elevated CO2 contents in the C–T atmosphere, it is doubtful if volcanism alone could have released enough CO2 to cause the higher temperatures calculated to exist at this time (Self et al. this issue). However, it is likely that a complex positive ELEMENTS Diagrams showing changes in key environmental indicators, sea level, and oceanic crust production between 110 and 80 Ma. The dotted horizontal line represents the Cenomanian– Turonian boundary (CTB). Diagram updated from Kerr (1998). FIGURE 2 feedback mechanism triggered by the volcanically derived CO2 led to increased CO2 and elevated temperatures (FIG. 3). The initial emission of CO2 from oceanic plateau volcanism was probably accompanied by the release of a considerable amount of SO2 and halogens (Self et al. this issue), which would have made the oceans locally more acidic (FIG. 3). This increased acidity would have led to the dissolution of shallow-water carbonates, thus releasing more CO2 to the atmosphere. [Significantly, Arthur et al. (1987) have noted that the C–T boundary is characterised by a lack of carbonates.] Thus, the addition of carbonate-derived CO2 plus volcanic CO2 to the atmosphere at the C–T boundary would have caused global warming of both the atmosphere and the oceans. Since the solubility of CO2 in seawater decreases by 4% for every 1°C rise in temperature, warming would have resulted in the release to the atmosphere of yet more CO2 which was previously dissolved in the oceans. Thus, a positive CO2 feedback mechanism would have been established (FIG. 3). Kerr (1998) has proposed that such a scenario would relatively rapidly result in the establishment of a runaway greenhouse effect. 290 D ECEMBER 2005 Increased atmospheric CO2 levels, in combination with disrupted oceanic circulation patterns and associated upwelling of nutrients from the deep ocean, would have resulted in increased biogenic productivity in ocean surface waters (FIG. 3). This increased biological activity led to removal of CO2 from the atmosphere and provided a mechanism for reducing the amount of atmospheric CO2. The δ13C peak in shallow ocean sediments at the C–T boundary reflects increased burial of marine organic carbon in the oceans and is due to the preference of organic matter for isotopically light carbon. The decrease in 87Sr/86Sr in the stratigraphic record (from 0.70753 to 0.70735), which started in the late-Cenomanian and continued until the mid-Turonian (FIG. 2), may be a reflection of the addition to seawater of hydrothermal fluids with a low 87Sr/86Sr from oceanic plateau volcanism. Conversely, the rise in 87Sr/86Sr from the mid-Turonian onwards may signify increased continental weathering resulting from global warming and its associated climatic disturbance. Continental weathering is another mechanism which can reduce the amount of atmospheric CO2. Higher oceanic temperatures would also have contributed to oceanic anoxia since the solubility of O2 in seawater decreases by 2% for every 1°C temperature rise (de Boer 1986). However, given that globally averaged ocean temperatures appear to have increased by at most 6°C (FIG. 2), the consequent ~10% reduction in the solubility of O2 in seawater is not enough to explain widespread oceanic anoxia. Several additional mechanisms by which oceanic plateaus can contribute to the depletion of dissolved O2 have been discussed by Sinton and Duncan (1997). The first of these is the reduction of dissolved O2 in seawater by the reaction of trace metals and sulphides in hydrothermal fluids with the O2. Although basaltic lava flows can be oxidised by hydrothermal fluids, both during and after eruption, this process is volumetrically insignificant when compared to the much greater effect of the oxidation of metals in hydrothermal fluids in lowering the amount of dissolved oxygen in seawater (FIG. 3). The eruption of a 1 × 104 km3 oceanic plateau basalt lava flow would release a similar volume of hydrothermal fluids at 350°C into the ocean (Cathles, cited in Sinton and Duncan 1997). Sinton and Duncan (1997) have calculated that the complete oxidation of the ELEMENTS Flow diagram of the likely physical and chemical environmental effects of oceanic plateau formation (see text for a detailed description). FIGURE 3 Fe2+, Mn2+, H2S, and CH4 in 1 x 104 km3 of hydrothermal fluid would use up ~6% of the total dissolved oxygen in the present-day ocean. However, as we have seen, the C–T ocean was significantly warmer and contained less dissolved oxygen than the present-day ocean. Therefore, the proportion of dissolved oxygen removed by 1 × 104 km3 of hydrothermal fluid at the C–T boundary would have been significantly greater than 6%. Another mechanism for removing dissolved oxygen from seawater, as discussed by Sinton and Duncan (1997), is the stimulation of the growth of living organisms (organic productivity) in the oceans by the injection of hydrothermal iron into surface waters. Vogt (1989) has suggested that hydrothermal plumes, even those several orders of magnitude smaller than 1 × 104 km3, would have been capable of rising into oceanic surface waters. Thus, as noted by Sinton and Duncan (1997), a large (1 × 104 km3) hydrothermal plume (with a low brine content) could easily rise through the water column and spread laterally over a significant proportion of the ocean surface. The trace metal–rich waters of such massive hydrothermal plumes may well have stimulated increased levels of organic productivity in nutrient-poor surface waters (Sinton and Duncan 1997). Coale et al. (1996) have shown that the addition of Fe into ocean surface waters can result in a rapid increase in the amount of phytoplankton. If a similar hydrothermal fluid–induced phytoplankton bloom occurred around the C–T boundary, the net effect would have been a further reduction in the amount of dissolved O2 as organic material decayed and sank through the seawater column (FIG. 3). FURTHER LINKS BETWEEN OCEANIC PLATEAU VOLCANISM AND ENVIRONMENTAL DISTURBANCE The link between oceanic plateau volcanism and global oceanic anoxia is given further credence by the occurrence of Aptian (124–112 Ma) black shales, which probably represent one of the most extensive concentrations of organicrich black shales in the geological record (Jenkyns 1980; 291 D ECEMBER 2005 Hallam 1987; Bralower et al. 1993). It is no coincidence that one of the most extensive periods of plume-related oceanic plateau formation occurred in the Pacific and Indian oceans during this period, including the Ontong Java Plateau, Hess Rise, Manihiki Plateau, the East Mariana and Nauru basins and a significant proportion of the Kerguelen Plateau (Eldholm and Coffin 2000). Although many of the chemical and physical characteristics of the Aptian oceanic anoxic event are very similar to those of the C–T boundary, one of the black shale horizons in the early Aptian exhibits a sharp decrease in δ13C, unlike the C–T boundary, which shows a sharp increase in δ13C (Jahren 2002). Present-day methane hydrates buried in ocean floor sediments possess very low δ13C (around –60‰). Thus the dissociation and catastrophic release of hydrates may have caused the sharp decrease in δ13C and contributed to global warming and oceanic anoxia in the early–mid Aptian (Jahren 2002). It has been proposed that methane release was triggered by tectonic events related to mantle plume uplift (Jahren 2002). However, while tectonic processes undoubtedly played a role, I contend that LIP-induced global warming was of greater importance and was probably of sufficient magnitude to cause dissociation of methane hydrates and consequent release of methane. This release would have accelerated global warming and anoxia since methane is a much more potent greenhouse gas than carbon dioxide. Furthermore, atmospheric oxidation of methane would consume a significant amount of free oxygen. Methane release may also have occurred around the C–T boundary, but its distinctive? δ13C signal may have been diluted by higher δ13C resulting from volcanism REFERENCES Arthur MA, Schlanger SO, Jenkyns HC (1987). The Cenomanian-Turonian oceanic anoxic event; II: Palaeoceanographic controls on organic-matter production and preservation. In: Brooks J, Fleet AJ (eds) Marine Petroleum Source Rocks. Geological Society of London Special Publication 26, pp. 401-420 Berner RA (1994) Geocarb II: a revised model of atmospheric CO2 over Phanerozoic time. American Journal of Science 294: 56-59 Bralower TJ, Sliter WV, Arthur MA, Lekie RM, Allard D, Schlanger SO (1993) Dysoxic/anoxic episodes in the AptianAlbian (Early Cretaceous). In: Pringle MS, Sager WW, Sliter WV, Stein S (eds) The Mesozoic Pacific: Geology, Tectonics, and Volcanism, American Geophysical Union Monograph 77, pp. 5-37 Coale KH, Johnson KS, Fitzwater SE, Gordon RM, Tanner S, Chavez FP, Ferioli L, Sakamoto C, Rogers P, Millero F, Steinberg P, Nightingale P, Cooper D, Cochlan WP, Landry MR, Constantinou J, Rollwagen G, Trasvina A, Kudela R (1996) A massive phytoplankton bloom induced by an ecosystem-scale iron fertilisation experiment in the equatorial Pacific Ocean. Nature 383: 495-501 Condie KC, DesMarais DJ, Abbott D (2001) Precambrian superplumes and supercontinents: a record in black shales, carbon isotopes, and paleoclimates? Precambrian Research 106: 239-260 de Boer PL (1986) Changes in the organic carbon burial during the Early Cretaceous. In: Summerhayes CP, Shackleton NJ (eds) North Atlantic Palaeoceanography. Geological Society of London Special Publication 21, pp. 321-331 ELEMENTS (around –10‰). Alternatively, the late Cenomanian ocean may have been too warm for extensive methane deposits to accumulate. Increased oceanic volcanism as a cause of oceanic anoxia and the deposition of organic-rich sediments has important implications for the location of potential oil source rocks. It is likely that many of the world’s most important occurrences of mid-Cretaceous oil source rocks owe their existence to the formation of oceanic plateaus in the Pacific and Indian oceans and the resultant global anoxia. This is obviously an interesting model, but how applicable is it to older oceanic plateaus and black shale sequences? Major black shale deposits occur throughout the Mesozoic (Hallam 1987), and some of these correlate with oceanic plateau volcanism. For example, important Kimmeridgian to Tithonian (155–146 Ma) oil source rocks correlate with the formation of the Sorachi Plateau in the western Pacific (Kimura et al. 1994). Furthermore, the formation of Toarcian (187–178 Ma) black shales corresponds with the eruption of the Karoo, Ferrar and Weddell Sea large igneous province during the breakup of Gondwana (Riley and Knight 2001). Thus, global oceanic anoxia (and the consequent formation of oil source rocks) is frequently associated with the development of oceanic plateaus. It is contended that the formation of oceanic plateaus perturbs the oceanic and atmospheric environments and sets in motion a chain of events, often leading to global warming, oceanic anoxia, black shale deposition and ultimately mass extinction. . Eldholm O, Coffin MF (2000) Large igneous provinces and plate tectonics. In: Richards MA, Gordon RG, van der Hilst RD (eds) The History and Dynamics of Global Plate Motions, American Geophysical Union Monograph 121, pp. 309-326 Hallam A (1987) End-Cretaceous mass extinction event: argument for terrestrial causation. 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Journal of the Geological Society of London 155, pp 619-626 Kimura G, Sakakibara M, Okamura M (1994) Plumes in central Panthalassa? Deductions from accreted oceanic fragments in Japan. Tectonics 13: 905-916 292 Larson RL (1991) Geological consequences of superplumes. Geology 19: 963-966 Nadin PA, Kusznir NJ, Cheadle, MJ (1997) Early Tertiary plume uplift of the North Sea and Faeroe- Shetland Basins. Earth and Planetary Science Letters 148: 109-127 Riley TR, Knight KB (2001) Age of prebreak-up Gondwana magmatism. Antarctic Science 13: 99-110 Sepkoski JJ (1986) Phanerozoic overview of mass extinction. In: Raup DM, Japlonski D (eds) Pattern and Processes in the History of Life, Springer-Verlag, Berlin, pp. 277-295 Sinton CW, Duncan RA (1997) Potential links between ocean plateau volcanism and global ocean anoxia at the Cenomanian-Turonian boundary. Economic Geology 92: 836-842 Sliter WV (1989) Aptian anoxia in the Pacific Basin. Geology 17: 909-912 Summerhayes CP (1987) Organic-rich Cretaceous sediments from the North Atlantic. In: Brooks J, Fleet AJ (eds) Marine Petroleum Source Rocks, Geological Society of London Special Publication 26, pp. 301-316 Vogt PR (1989) Volcanogenic upwelling of anoxic, nutrient-rich water: A possible factor in carbonate-bank /reef demise and benthic faunal extinctions? Geological Society of America Bulletin 101: 1225-1245 Wignall PB (2001) Large igneous provinces and mass extinctions. Earth-Science Reviews 53: 1-33 Yurtsever TS, Tekin UK, Demirel IH (2003) First evidence of the Cenomanian/ Turonian boundary event (CTBE) in the Alakirçay Nappe of the Antalya Nappes, southwest Turkey. Cretaceous Research 24: 41-53 . D ECEMBER 2005