1 METAMORPHIC FLUIDS AND GLOBAL ENVIRONMENTAL CHANGES 2 3 Henrik Svensen and Bjørn Jamtveit 4 Physics of Geological Processes (PGP), University of Oslo, Norway. 5 Email: hensven@fys.uio.no. 6 7 Carbon dioxide is produced by metamorphic reactions in orogenic belts and high heat-flow 8 systems. Part of this carbon is ultimately released to the atmosphere, but the long 9 timescales of regional metamorphism implies that the short term effects on the 10 environment are minor. Here we show that contact metamorphism around igneous sill 11 intrusions in organic-rich sedimentary basins has the potential to generate huge volumes of 12 CH4 and CO2, and that these gases are rapidly released to the atmosphere via vertical pipe 13 structures. The high fluxes and volumes of greenhouse gases produced in this way, 14 indicates that metamorphic processes may have first order influence on global warming 15 and mass extinctions. 16 17 Keywords: Metamorphic carbon degassing, contact metamorphism, Large igneous provinces, 18 volcanic basins, rapid environmental changes 19 20 1 21 INTRODUCTION 22 Carbon-bearing fluids are constantly seeping from lithospheric sources to Earth’s surface and 23 atmosphere (e.g., KERRICK, 2001; MORNER and ETIOPE, 2002). In some places, such as young 24 mountain ranges and high heat-flow zones, the seepage is more intense than in others. In these 25 settings, fluid expulsion at the Earth’s surface is a reflection of metamorphism taking place many 26 kilometers below. Hot springs and mud pots are familiar surface manifestations of metamorphic 27 fluid production. The processes behind metamorphic production of C-rich volatiles include 28 reactions that transform carbonates, feldspar and quartz to amphibole, epidote, pyroxene, garnet, 29 and CO2 (e.g., KERRICK et al., 1991). Key question include how much and how fast CO2 can be 30 generated and released by metamorphic processes, and if the degassing can trigger rapid global 31 warming and thus have an impact on life on Earth? 32 Pioneer work by Derrill M. Kerrick and co-workers in the 1990’s attempted to link 33 Cenozoic greenhouse events (see ZACHOS et al., 2001) to large scale CO2 degassing generated by 34 prograde metamorphism of carbonate-bearing rocks (KERRICK et al., 1995; NESBITT et al., 1995). 35 It was proposed that contact metamorphism around plutons in western North American in the 36 Eocene released large amounts of metamorphic CO2 (0.167 Gt per km2 per m.y.) and that this 37 degassing could have contributed to the Eocene greenhouse conditions if more than 106 km2 38 underwent metamorphism (NESBITT et al., 1995; KERRICK and CALDEIRA, 1998). This much CO2 39 degassing would exceed CO2 consumption by silicate weathering (KERRICK and CALDEIRA, 40 1993). An Early Cenozoic climatic effect of CO2 degassing by Himalayan regional 41 metamorphism was however discarded (KERRICK and CALDEIRA, 1999), but new data suggests 42 that at least the present day regional metamorphism is a net supplier of CO2 to the atmosphere 43 (BECKER et al., 2008; EVANS et al., 2008). 2 44 The relatively short duration of Cenozoic greenhouse-gas driven events, which lasted less 45 that 200,000 years relative to the long duration of orogenesis is a major challenge for the 46 hypothesis that metamorphic CO2 affected climate. Several rapid global warming events and 47 mass extinctions are known from the geological record, including the Paleocene-Eocene thermal 48 maximum (PETM; 55 Ma), the Toarcian event (183 Ma), and the end-Permian (252 Ma) and the 49 Triassic-Jurassic (200 Ma) extinctions (e.g., WIGNALL, 2001; COURTILLOT and RENNE, 2003). 50 The triggering mechanisms of all these environmental events are poorly understood. Gas hydrate 51 dissociation, sluggish ocean circulation and anoxia, lava CO2 degassing, and metamorphic CH4 52 degassing are among the hypotheses that have been proposed (e.g., WIGNALL, 2001; COHEN et 53 al., 2007; KNOLL et al., 2007). However, the correlation in time between these events, the 54 formation of large igneous provinces (LIPs) and the contact metamorphism in sedimentary 55 basins intruded by the LIP magmas (Table 1) suggests a possible causal relationship. 56 57 VOLCANIC BASINS AND LIPs 58 Contact metamorphism in sedimentary basins occurs when hot and partly molten igneous 59 intrusions heat their country rocks. These basins are called volcanic basins, and the igneous 60 intrusions are often basaltic and emplaced during LIP formation. Volcanic basins are common 61 along volcanic rifted continental margins and on lithospheric cratons (Figure 1). The intrusions 62 commonly form sheet-like sills and dikes, and sill thicknesses can exceed 350 meters, 63 sandwiched between sedimentary sequences. As sedimentary basins are among the main crustal 64 reservoirs of organic and inorganic carbon (e.g., IPCC, 2007), there is a huge potential for CH4 65 and CO2 generation in volcanic basins. A link between contact metamorphism and the PETM 3 66 was suggested in 2004 based on detailed seismic imaging and borehole studies in the Vøring and 67 Møre basins, offshore Norway (SVENSEN et al., 2004), and this provided a new framework for 68 investigating the environmental consequences of metamorphism. The cornerstone of this 69 hypothesis is rapid gas generation from organic material and subsequent release of greenhouse 70 gases to the atmosphere. Recent results have provided strong evidence that a similar explanation 71 applies to other climate events including the Toarcian (Lower Jurassic), the Triassic-Jurassic, the 72 end-Permian, and the end-Guadalupian (e.g., MCELWAIN et al., 2005; BEERLING et al., 2007; 73 SVENSEN et al., 2007; RETALLACK and JAHREN, 2008; GANINO and ARNDT, 2009; SVENSEN et 74 al., 2009). This hypothesis is supported by geological constraints (e.g., observed contact 75 aureoles, sill intrusions, and vertical pipe structures) as well as the fact that metamorphism of 76 organic carbon leads to generation of 77 geochemical data than the emission of 12C -depleted mantle CO2 due to LIP lava degassing. 12 C-enriched CH4 which can better explain the available 78 79 CONTACT METAMORPHISM AND CARBON DEGASSING 80 Vast volumes of sedimentary rocks are heated in volcanic basins following sill emplacement 81 (Figure 1 and Table 2). Sill intrusions may extend laterally over several hundred kilometres, 82 commonly have thicknesses in the 50-200 meter range, and dominate the geology of sedimentary 83 basins (Figure 2A). Thus single sill intrusions may have volumes of 5,000-20,000 km3. 84 Considering that the thicknesses of metamorphic aureoles are commonly about the same as the 85 sill thickness (both below and above the sill), the volume of heated sediments could be as large 86 as 10-40,000 km3. Because the inner contact aureoles reach peak metamorphic conditions 87 (typically 400-500 °C) shortly after sill emplacement (10-500 years), the metamorphic reactions 4 88 and associated fluid production are also very fast. If only 1 wt. % of the organic carbon in shale 89 or siltstone is transformed into gaseous carbon compounds, the gas production potential 90 associated with a 5,000-20,000 km3 sill intrusion is 230-920 Gt C (corresponding to 310-1200 Gt 91 CH4). This means that a single melt batch injected into an organic-rich sedimentary basin can 92 generate sufficient methane, rapidly enough, to cause global warming. 93 In volcanic basins there is abundant evidence for rapid injection of the aureole generated 94 gases into the atmosphere. This process is initiated by local overpressure within the sediments. 95 When sedimentary host rocks are heated by magma intrusion, decomposition of organic matter, 96 mineral dehydration (generating H2O and CO2), and pore fluid expansion or boiling occur on a 97 timescale of years. The resulting overpressure may lead to hydrofracturing and the formation of 98 breccia pipes and hydrothermal vent complexes (e.g., JAMTVEIT et al., 2004). In the Karoo Basin, 99 South Africa, the hydrothermal vent complexes commonly crops out in the uppermost 400-500 100 meters of the basin (Figure 2). In addition, numerous breccia pipes are rooted in black shale 101 contact aureoles at deeper basin levels, demonstrating that high pore fluid pressures may also 102 developed during rapid decomposition of organic matter to carbon gases (SVENSEN et al., 2007). 103 Baked grey shales that have lost the organic carbon remain in the pipes (Figure 3). Vent 104 structures and breccia pipes are characteristic features of many volcanic basins including the 105 Vøring and Møre basins, the Faroe-Shetland Basin, and the Tunguska Basin (Figure 1; Table 1). 106 In the Tunguska Basin in Siberia, spectacular pipes with up to 1.6 km wide subaerial explosion 107 craters formed during the end-Permian. A schematic cross section of a volcanic basin with pipe 108 structures is shown in Figure 4. In marine settings, like in the Vøring Basin, the craters can reach 109 a size of more than 10 km in diameter (PLANKE et al., 2005). 110 5 111 SEDIMENT COMPOSITION AND ENVIRONMENTAL EFFECTS 112 The chemical composition of the sedimentary rocks heated by igneous intrusions has a profound 113 influence on the metamorphic fluid composition (e.g., SVENSEN et al., 2004; GANINO and 114 ARNDT, 2009; SVENSEN et al., 2009). An overview of the sediment-types heated in various 115 volcanic basins is given in Table 2. For instance, organic-rich shale generates CH4 during contact 116 metamorphism, whereas coal generates fluids with CO2. In addition, water is generated. Since 117 many sedimentary basins contained hydrogen rich kerogen and oil and gas accumulations at the 118 time of sill emplacement, petroleum-derived gases like CH4 and C2H6 may have dominated the 119 metamorphic fluid. If limestones or dolostones are heated, the generated fluid will be dominated 120 by 121 evaporites with anhydrite and rock salt may generate SO2 and HCl, and if organic matter or 122 petroleum is present, CH4 and halocarbons such as CH3Cl and CH3Br may also form. This was 123 recently confirmed by experiments in which natural rock salt from the Tunguska Basin in East 124 Siberia was heated to 275 °C in order to simulate contact metamorphism. Halocarbons were 125 among the detected gases, and they were generated by reactions between petroleum-bearing fluid 126 in inclusions and the host salt (SVENSEN et al., 2009). 13 C-enriched CO2, or 13 C-depleted CH4 if organic matter or graphite is present. Moreover, 127 In East Siberia, a major sill emplacement event took place at the end of the Permian, and 128 thick sills are present throughout the basin. Mass balance calculations suggest that 10,000-30,000 129 Gt C could have been generated during contact metamorphism of organic matter, accompanied 130 by 4,500-13,000 Gt CH3Cl (SVENSEN et al., 2009). The presence of hundreds of pipe structures 131 rooted in evaporite lithologies suggests that the gases were released to the atmosphere. Thus the 132 end-Permian global warming event could have been triggered by aureole degassing. Moreover, 133 recent atmospheric modelling shows that >1000 Gt of methyl chloride are required to cause 6 134 significant stratospheric ozone depletion over a 100,000 year time scale (BEERLING et al., 2007). 135 This may explain some of the terrestrial consequences of the end-Permian mass extinctions, as 136 mutated pollen are ascribed to ozone layer breakdown and damaging UV-B radiation (VISSCHER 137 et al., 2004). 138 139 CONTACT VS REGIONAL METAMORPHISM 140 The 5-10 million year timescale of orogeny or crustal extension cannot explain rapid and 141 transient climatic events, and thus regional metamorphism is unlikely to affect short term global 142 climate changes. Moreover, other lines of evidence suggest that release of CO2 due to carbonate 143 metamorphism played a minor role in Cenozoic global climate changes. The main reason is that 144 metamorphism of carbonates generates 145 shows that the carbon responsible for Eocene global warming was 12C-enriched in terms of 13C 146 (e.g., DICKENS et al., 1997; ZACHOS et al., 2001). Contact metamorphism in volcanic basins is a 147 far more likely explanation to the observed transfer of CH4 and CO2 from the lithosphere to the 148 atmosphere on short timescales. 12 C-depleted CO2 whereas available geological data 149 150 Acknowledgments 151 This study was supported by a Centre of Excellence grant to PGP, by a Young Outstanding 152 Researcher grant and a PetroMaks grant to H. Svensen, all from the Norwegian Research 153 Council. We thank Sverre Planke for introducing us to volcanic basins, and for providing figures 154 1 and 2A. 7 155 156 References 157 158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 194 195 196 Becker, J. A., Bickle, M. J., Galy, A., and Holland, T. J. B., 2008. Himalayan metamorphic CO2 fluxes: Quantitative constraints from hydrothermal springs. Earth and Planetary Science Letters 265, 616-629. Beerling, D. J., Harfoot, M., Lomax, B., and Pyle, J. A., 2007. The stability of the stratospheric ozone layer during the end-Permain eruption of the Siberian Traps. Philosophical Transactions of the Royal Society a-Mathematical Physical and Engineering Sciences 365, 1843-1866. Cohen, A. S., Coe, A. L., and Kemp, D. B., 2007. The late Palaeocene-Early Eocene and Toarcian (Early Jurassic) carbon isotope excursions: a comparison of their time scales, associated environmental changes, causes and consequences. Journal of the Geological Society 164, 1093-1108. Courtillot, V. E. and Renne, P. R., 2003. On the ages of flood basalt events. Comptes Rendus Geoscience 335, 113-140. Dickens, G. R., Castillo, M. M., and Walker, J. C. G., 1997. A blast of gas in the latest Paleocene: simulating first-order effects of massive dissociation on oceanic methane hydrate. Geology 25, 259-262. Evans, M. J., Derry, L. A., and France-Lanord, C., 2008. Degassing of metamorphic carbon dioxide from the Nepal Himalaya. Geochem. Geophys. Geosyst. 9. Ganino, C. and Arndt, N. T., 2009. Climate changes caused by degassing of sediments during the emplacement of large igneous provinces. Geology 37, 323-326. IPCC, 2007. Climate Change 2007. Fourth Assessment Report (AR4). Intergovernmental Panel on Climate Change, Geneva, 2007. Jamtveit, B., Svensen, H., Podladchikov, Y., and Planke, S., 2004. Hydrothermal vent complexes associated with sill intrusions in sedimentary basins, Physical geology of high-level magmatic systems. Geological Society Special Publication, London. Kerrick, D. M., 2001. Present and past nonanthropogenic CO2 degassing from the solid Earth. Reviews of Geophysics 39, 565-585. Kerrick, D. M. and Caldeira, K., 1993. Paleoatmospheric consequences of CO2 released during Early Cenozoic regional metamorphism in the Tethyan orogen. Chemical Geology 108, 201-230. Kerrick, D. M. and Caldeira, K., 1998. Metamorphic CO2 degassing from orogenic belts. Chemical Geology 145, 213-232. Kerrick, D. M. and Caldeira, K., 1999. Was the Himalayan orogen a climatically significant coupled source and sink for atmospheric CO2 during the Cenozoic? Earth and Planetary Science Letters 173, 195-203. Kerrick, D. M., Lasaga, A. C., and Raeburn, S. P., 1991. Kinetics of heterogeneous reactions. Reviews in Mineralogy 26, 583-671. Kerrick, D. M., McKibben, M. A., Seward, T. M., and Caldeira, K., 1995. Convective hydrothermal CO2 emission from high heat flow regions. Chemical Geology 121, 285293. 8 197 198 199 200 201 202 203 204 205 206 207 208 209 210 211 212 213 214 215 216 217 218 219 220 221 222 223 224 225 226 227 228 229 230 231 232 233 234 235 236 237 238 239 Knoll, A. H., Bambach, R. K., Payne, J. L., Pruss, S., and Fischer, W. W., 2007. Paleophysiology and end-Permian mass extinction. Earth and Planetary Science Letters 256, 295-313. McElwain, J. C., Wade-Murphy, J., and Hesselbo, S. P., 2005. Changes in carbon dioxide during an oceanic anoxic event linked to intrusion into Gondwana coals. Nature 435, 479-482. Morner, N. A. and Etiope, G., 2002. Carbon degassing from the lithosphereSymposium on Global Carbon Cycle and Its Changes over Glacial-Intergiacial Cycles, Strasbourg, France. Nesbitt, B. E., Mendoza, C. A., and Kerrick, D. M., 1995. Surface fluid convection during Cordilleran extension and the generation of metamorphic CO2 contributions to Cenozoic atmospheres. Geology 23, 99-101. Planke, S., Rassmussen, T., Rey, S. S., and Myklebust, R., 2005. Seismic characteristics and distribution of volcanic intrusions and hydrothermal vent complexes in the Vøring and Møre basins. In: Dore, T. and Vining, B. Eds.)Petroleum Geology: North-West Europe and Global Perspectives - Proceedings of the 6th Petroleum Geology Conference. Geological Society Publishing House, London. Polteau, S., Mazzini, A., Galland, O., Planke, S., and Malthe-Sorenssen, A., 2008. Saucer-shaped intrusions: Occurrences, emplacement and implications. Earth and Planetary Science Letters 266, 195-204. Retallack, G. and Jahren, A. H., 2008. Methane Release from Igneous Intrusion of Coal during Late Permian Extinction Events. The Journal of Geology 116, 1-20. Svensen, H., Jamtveit, B., Planke, S., and Chevallier, L., 2006. Structure and evolution of hydrothermal vent complexes in the Karoo Basin, South Africa. Journal of the Geological Society 163, 671-682. Svensen, H., Planke, S., Chevallier, L., Malthe-Sorenssen, A., Corfu, F., and Jamtveit, B., 2007. Hydrothermal venting of greenhouse gases triggering Early Jurassic global warming. Earth and Planetary Science Letters 256, 554-566. Svensen, H., Planke, S., Malthe-Sorenssen, A., Jamtveit, B., Myklebust, R., Rasmussen Eidem, T., et al., 2004. Release of methane from a volcanic basin as a mechanism for initial Eocene global warming. Nature 429, 542-545. Svensen, H., Planke, S., Polozov, A. G., Schmidbauer, N., Corfu, F., Podladchikov, Y. Y., et al., 2009. Siberian gas venting and the end-Permian environmental crisis. Earth and Planetary Science Letters 277, 490-500. Visscher, H., Looy, C. V., Collinson, M. E., Brinkhuis, H., Cittert, J., Kurschner, W. M., et al., 2004. Environmental mutagenesis during the end-Permian ecological crisis. Proceedings of the National Academy of Sciences of the United States of America 101, 12952-12956. Wignall, P. B., 2001. Large igneous provinces and mass extinctions. Earth-Science Reviews 53, 1-33. Zachos, J., Pagani, M., Sloan, L., Thomas, E., and Billups, K., 2001. Trends, rhythms, and aberrations in global climate 65 Ma to present. Science 292, 686-693. Figures 9 240 241 242 Figure 1. Overview of large igneous provinces (basalts in red) and volcanic basins. The basalts 243 are lava flows from the LIPs whereas the sub-volcanic part of the provinces, with sills and dikes, 244 are outlined with heavy lines. The volcanic basins mentioned here are indicated with black 245 outlines, and other major volcanic basins with a black circle. 246 10 247 248 249 Figure 2. Sill intrusions and pipes in the Karoo Basin, South Africa. A) The Golden Valley sill 250 complex with its saucer-shaped intrusions (see POLTEAU et al., 2008). The dolerite sills are about 251 100 meters thick and are emplaced in sandstones and mudstones. Sill intrusions are associated 252 with all the hills in the background. Photo: Sverre Planke. B) Breccia pipes from the 253 Loriesfontein area in the western parts of the basin. The pipes are seen as black dots with light 254 grey circular alteration haloes. A dirt road in the lower half of the image gives the scale. C) The 255 Witkop III hydrothermal vent complex (SVENSEN et al., 2006) is a crater that formed at the 256 Lower Jurassic paleosurface due to release of fluid from contact aureoles. 257 11 258 259 Figure 3. Photograph of a drill core showing contact metamorphism of black shale from within a 260 breccia pipe in the Calvinia area in western Karoo Basin (SVENSEN et al., 2007). The original 261 shale was black in color and contact metamorphism resulted in transformation of the organic 262 matter to gas and a change in color. The secondary bleaching of the sample is due to reactions 263 with hydrothermal fluids within the breccia, and the precipitation of sulfides. 264 12 265 266 Figure 4. Schematic cross section of a sill intrusion with associated contact aureole and 267 hydrothermal vent complex. 268 269 13 Table 1. Major volcanic basins, LIPs, and environmental changes. Volcanic Basin LIP Sill age (Ma) Event 270 Vøring and Møre (Norway) North East Atlantic 55.6 PETM Karoo (South Africa) Karoo-Ferrar 182.6 Toarcian Amazonas (Brazil) CAMP ~200 Triassic-Jurassic boundary Solimoes (Brazil) CAMP ~200 Triassic-Jurassic boundary Tunguska (Russia) Siberian Traps ~252 Permian-Triassic boundary Sichuan (China) Emeishan Traps ~261 End-Guadalupian Abbreviations: CAMP: Central Atlantic Magmatic Province; CIE: Carbon isotope excursion. Pipe structures yes yes ? ? yes ? CIE yes yes yes yes yes yes Mass extinction minor minor major major major major 271 272 Table 2. Key facts about volcanic basins. Volcanic Basin Area with sills 1000 km2 Vøring and Møre (Norway) 85 Karoo (South Africa) 390 Amazonas (Brazil) 200 Solimoes (Brazil) 600 Tunguska (Russia) 2000 Sichuan (China) 200 Sills in black shale yes yes yes yes yes ? Sills in evaporite no no yes yes yes no Sills in carbonates no no yes yes yes yes 273 14