Geologic carbon cycle Textbook chapter 5, 6 & 14 Global carbon cycle Long-term stability and feedback

Geological carbon cycle Weathering of rocks Volcanic degassing Sediment burial Williams and Follows (2011)

Volcanic degassing Volcano Hydrothermal vents Very approximate carbon flux ~ 0.04 GTC/year Small carbon source relative to human emission, air-sea CO2 exchange, biological productivity BUT it is dominant over long timescales ~ millions of years+

Volcanic degassing Equation for Ocean/Atmosphere Carbon Inventory Steady State Timescale Residence Time

Residence time (Residence time) = (Inventory) / (Flux) Volcanic degassing 0.04 GTC/year Ocean-atmosphere system ~ 40,000 GTC

Weathering Physical Weathering = mechanical breakdown of rocks Erosion Formation of sediments Chemical Weathering = chemical breakdown Salinity Some nutrients (silicate, phosphate) Alkalinity (Ca2+) Carbonate Rocks 1. Carbon dioxide is removed from the atmosphere by dissolving in water and forming carbonic acid CO2 + H2O -> H2CO3 (carbonic acid) 2. Carbonic acid is used to weather rocks, yielding bicarbonate ions, other ions, and clays H2CO3 + H2O + silicate minerals -> HCO3- + cations (Ca++, Fe++, Na+, etc.) + clays 3. Calcium carbonate is precipitated from calcium and bicarbonate ions in seawater by marine organisms like coral Ca++ + 2HCO3- -> CaCO3 + CO2 + H2O the carbon is now stored on the seafloor in layers of limestone

Weathering of Carbonate Rocks 1. Carbon dioxide is removed from the atmosphere by dissolving in water and forming carbonic acid CO2 + H2O -> H2CO3 (carbonic acid) 2. Carbonic acid is used to weather rocks (e.g. rain), yielding bicarbonate ions, other ions, and clays, which are dumped into ocean (e.g. river runoff) H2CO3 + H2O + silicate minerals -> HCO3- + cations (Ca++, Fe++, Na+, etc.) + clays 3. Calcium carbonate is precipitated from calcium and bicarbonate ions in seawater by marine organisms like coral, coccolithophores, foraminifera Ca++ + 2HCO3- -> CaCO3 + CO2 + H2O (form both calcite and aragonite) the carbon is now stored on the seafloor in layers of limestone

Formation of sediments Erosion and sediment transport Grain size scales and energy conditions

Seafloor sediments Plankton origin marine snow Land origin

CCD = Calcite Compensation Depth Hard shell component of the marine snow Solubility of calcite depends on the pressure Calcite tends to dissolve in the deep ocean Above CCD, calcite is preserved in the sediment Below CCD, calcite is dissolved and not preserved in the sediment

Thermodynamic stability of CaCO3 Solubility product Ksp Ksp increases with pressure Supersaturation above the calcite saturation horizon Undersaturation below the Sarmiento and Gruber (2006)

Distribution of calcite on the seafloor Chapter 5, Fig 17

Stability of calcite and pH Combination of DIC and Alk controls the acidity of seawater. Increasing DIC increases acidity and lowers [CO32-]. Once [CO32-] goes down below the thermodynamic threshold [CO32-]sat, calcite is undersaturated and dissolves in the water

Carbonate weathering cycle CaCO3 (land)  Ca2+ + CO32- (river input to the ocean)  Formation of marine snow  CaCO3 (sediment) In a steady state (geological), no net addition of alkalinity or DIC to the ocean-atmosphere system

Carbonate deposits The sink becomes the source CaCO3 deposit from coccolith-rich sedimentary rock

Silicate weathering cycle CaSiO3(land)+CO2(air) SiO2 + Ca2+ + CO32- (river input)  SiO2(sediment) + CaCO3(sediment) Silicate weathering absorbs CO2 from the atmosphere, and bury it into the sediment  Net removal of CO2

Biogenic silica on the seafloor sediments Chapter 5, Fig 15

Silica distribution in the surface ocean Sarmiento and Gruber (2006)

Silicate weathering and CO2 Volcanism  CO2 to the atmosphere Chemical breakdown of silicate rock  CO2 into the ocean Burial of CaCO3  Plate tectonics  Subduction zone

Faint young sun paradox Sagan and Mullen (1972): In the early Earth, the solar energy input was only about 70% of today but the climate was as warm as today. Long-term stability of the Earth’s climate system Temperature remained within 0°C and 100°C

Weathering-CO2 feedback Hypothesis: The speed of rocks’ chemical breakdown partly depends on the temperature. Cold climate tends to slow down chemical weathering Slow-down of silicate weathering cannot balance volcanic CO2 flux Climate warms up due to increased atmospheric CO2 Weathering-CO2 feedback tends to stabilize the climate temperature over millions of years Is this sufficient to explain the early Earth’s warmth? Rosing et al., (2010) Nature: ongoing debate

Evidence for the weathering CO2 feedback? Ice core pCO2 for the last 800,000 years Very little long term trend

Modulation of weathering CO2 feedback Volcanic CO2 input The rate of plate subduction Calcite composition of subducting seafloor Weathering of silicate rock Mountain building Continent distribution Sea level Vegetation on land

Burial of organic carbon Sink of atmospheric CO2 Removal of reduced carbon  Source of atmospheric O2 Origin of fossil fuel

Photosynthesis and respiration Simplified representation of photosynthesis Most of the CH2O will return to CO2 via aerobic respiration Energy source for living organisms Small fraction of CH2O is buried on land and in the ocean sediments Increases atmospheric O2

Long-term controls on atmospheric O2 Great O2 event = 2.5 billion years ago Early atmosphere had no oxygen. Oxygenation of the planet by biological O2 production O2 supports more complex, multi-cellular life Burial of organic matter balances organic C weathering

Organic Carbon-O2 feedback Hypothesis: Burial of organic carbon depends on the oxygen content of the deep ocean If atmospheric O2 gets low, deep water goes anoxic Aerobic respiration stops and the respiration of organic matter decreases More organic matter are preserved in the sediment Increases atmospheric O2 This feedback can potentially stabilize the atmospheric oxygen No quantitative model/theory yet

CaCO3 – pH feedback Why ocean pH is about 8?  Carbonate chemistry DIC and alkalinity of seawater set pH of the seawater [CO32-] (≈ Alk – DIC) increases with pH CaCO3-pH feedback If the ocean pH gets low, more CaCO3 dissolves at the seafloor. Dissolution of CaCO3 increases Alk relative to DIC pH increases

Fate of fossil fuel CO2 CO2 emission into the atmosphere by human activities (decades) Partial absorption into the land and upper ocean (decades) O(100-1,000 years) Equilibration of deep ocean carbon reservoir Absorbs 85% of carbon emission O(10,000+ years) Dissolution of seafloor CaCO3 Increases alkalinity Absorbs remaining 15%

Theme III: long-term carbon-climate relation Three stabilizing mechanisms for temperature, CO2, alkalinity and pH of the seawater Operates over plate tectonic timescales, providing stability to the climate and biogeochemical cycles Weathering-CO2 feedback Silicate weathering Organic Carbon-O2 feedback Preservation of organic matter on the seafloor CaCO3-pH feedback Preservation of CaCO3 on the seafloor

Changing mood of carbon cycle O(10-1k years) Ocean carbon cycle acts as a sink of carbon and heat, moderating the climate change O(100k years) Ocean carbon cycle seems to act as an amplifier of the glacial-interglacial climate change O(1 million years) Ocean carbon cycle seems to stabilize the climate and cycling of elements through the three feedbacks… Further reading: D. Archer (2010) “The Global Carbon Cycle”, Princeton University Press.