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Major chemical cycles • GOAL: Use changes in the ratios of isotopes of carbon (C) and oxygen (O) to help reconstruct Earth history Earth History, Ch. 10 1 Major chemical cycles • Changes in 13C/12C ratio in rocks and fossils are related to changes in rate of organic burial, which influence CO2 and O2 in Earth’s atmosphere • Changes in 18O/16O ratio in rocks and fossils are related to glacial ice volume (i.e., changes in Earth’s temperature Earth History, Ch. 10 2 Carbon and Oxygen Isotopes Element Carbon Oxygen atomic number 6 8 12 13 14 total relative abundance (%) 98.890 1.110 trace 100.000 16 17 18 total 99.789 0.007 0.204 100.000 atomic weight Earth History, Ch. 10 3 Isotope ratios— “δ” notation [(13C/12C)sample – (13C/12C)standard] δ13C = × 1000 (13C/12C)standard [(18O/16O)sample – (18O/16O)standard] δ18O = × 1000 (18O/16O)standard (13C/12C)standard is a piece of belemnite (18O/16O)standard is “mean” ocean water Earth History, Ch. 10 4 Mass spectrometer Measures 18O/16O and 13C/12C ratios in CO2 gas, usually derived from a mineral grain Earth History, Ch. 10 5 Isotope fractionation • CO2 and O2 continuously cycle through the atmosphere and biosphere as a consequence of photosynthesis and respiration, BUT… Earth History, Ch. 10 6 Isotope fractionation (cont.) • …some processes preferentially use certain isotopes and not others (fractionation) • CO2 in plants is enriched in 12C (plants are “isotopically light”) • H2O in water vapor is enriched in 16O (rain and snow are “isotopically light”) Earth History, Ch. 10 7 Isotope fractionation (cont.) • Fractionation would be unimportant, except that the C and O “budgets” can be thrown out of balance by “sinks” • Buried organic matter is a “sink” for light carbon – Accumulation of buried organic matter isotopically heavier CO2 everywhere else • Continental glaciers are a “sink” for light oxygen – Accumulation of glacial ice isotopically heavier O2 everywhere else Earth History, Ch. 10 8 A. Burial rate of carbon balances oxidation rate B. Burial rate of carbon exceeds oxidation rate Carbon “sink” Earth History, Ch. 10 9 Oxygen “sink” Earth History, Ch. 10 10 High rate of decomposition (oxidation) consumes O2 High rate of burial prevents decomposition (oxidation), resulting in more atmospheric O2 Earth History, Ch. 10 11 The Carbon isotope record Burial of organic carbon in Carboniferous coal swamps Earth History, Ch. 10 12 Historical trends in atmospheric O2 Carboniferous peak in abundance of oxygen Large amount of buried organic matter means less oxygen being used in organic decay (oxidation) Earth History, Ch. 10 13 High rate of decomposition (oxidation) releases CO2 Earth History, Ch. 10 High rate of organic burial prevents decomposition, which reduces the amount of atmospheric CO2 14 Historical trends in atmospheric CO2 Devonian decline in abundance of CO2 Diversification of land plants caused increase in rates of mineral weathering processes, which consume CO2 Decline in atmospheric CO2 may have led to global cooling Earth History, Ch. 10 15 The Oxygen isotope record glacial intervals When glaciers lock up light oxygen, the residual seawater is isotopically heavy. Thus, CaCO3 marine shells will be isotopically heavy during ice ages Earth History, Ch. 10 16