1. The Carbon Cycle The carbon cycle describes the exchange of carbon atoms between various reservoirs within the earth system. The carbon cycle is a geochemical cycle and since it involves the biosphere it is sometimes referred to as a bio-geochemical cycle. Other biogeochemical cycles involve oxygen, nitrogen and sulfur. 

2. Why study the carbon cycle? • to learn why atmospheric carbon dioxide has tended to decrease over the lifetime of the earth and why it underwent large swings between glacial and interglacial periods of the ice ages • to learn why atmospheric carbon dioxide is increasing at only about half the rate that one would expect, given the current rate of burning fossil fuels  • to predict future concentrations of atmospheric carbon dioxide  • to assess the potential of carbon 'sequestration' (planting new trees) as a strategy for slowing the buildup of atmospheric carbon dioxide

3. Basic concepts • reservoirs - forms in which carbon resides within the earth system- usually expressed in terms of the mass of carbon in Gigatons (Gt) = Petagram (Pg) • transfer mechanisms - processes that move carbon between reservoirs - they usually involve a physical process and a chemical reaction • transfer rate - expressed in terms of Pg per year  • residence time for carbon in a reservoir - estimated by dividing the amount of carbon in that reservoir by the transfer rates in and out of it.  For example, the residence time for atmospheric carbon dioxide is 760 Pg divided by 60 Pg/year yields ~13 years

4. S total flux out of the reservoir M content if a substance in the reservoir Turnover Time, renewal time single reservoir with source flux Q, sink flux S, and content M Q S=kM M The equation describing the rate of change of the content of a reservoir can be written as

5. Atmosphere 725 (Annual increase ~3) Deforestation ~1 ~93 ~90 ~60 ~120 ~1 Surface water Dissolved inorg. 700 Dissolved org. 25 (Annual increase ~ 0,3) Short-lived biota ~110 ~15 Long-lived biota ~450 (Annual decrease ~1) ~15 ~40 Detritus decomposition 54-50 Primary production ~40 Respiration & decomposition ~36 Litter ~60 ~40 ~38 Surface biota 3 2 - 5 ‹1 Detritus ~4 2 - 5 Intermediate and Deep water Dissolved inorg. 36,700 Dissolved org. 975 (Annual increase ~ 2,5) Soil 1300 - 1400 (Annual decrease ~1) Peat (Torf) ~160 ‹1 5 Fossil fuels oil, coal, gas 5,000 - 10,000 Land Sea Fig. 4-3 principal reservoirs and fluxes in the carbon cycle. Units are 1015 g(Pg) C (burdens) and PgC/yr (fluxes). (From Bolin (1986) with permission from John Wiley and Sons.)

8. Seawater Carbonate System imgres

9. Alkalinity is the measure of the pH- buffering capacity of the water • Sum ( neg. charges) = Sum (pos. charges) • Conservative ions do not undergo acid-base reactions: Na+,K+,Ca2+,Cl- • Non-conservative ions: H+,OH-,HCO3-,CO32- • Alk= Sum ( neg. charges for non-conservative ions) - Sum (pos. charges for non-conservative ions)

10. The 'mg/l CaCO3' unit reports the concentration of CaCO3 in pure water that would provide the same buffering capacity as the water sample in question. This does not mean the sample contains that much CaCO3.   In fact, it tells you nothing about how much of the buffering is due to carbonates, it is only a measure of equivalency. • 1 meq/l = 2.8 dKH = 50 mg/l CaCO3 

11. Global mean seawater properties Approximations:

12. What controls the pCO2 ?

13. What controls the pCO2 ? Sensitivity of pCO2 to changes in DIC, Buffer factor, Revelle factor ca. 10

14. pH pCO2 m eq mol/kg Buffer factor m mol/kg

15. DIC: mmol/kg to Pg • DIC= 2.35 mmol/kg seawater • Volume Oceans= 1370 e15 m^3 • Rho_water= 1000 kg/m^3 • Mass_water= 1370 e18 kg • DIC for Oceans: 3220 e15 mol • DIC carbon: 3220 e15 mol x 12 g/mol=38640 Pg mol = 6.023 molecules (of a molecular substance), or atoms (of an element), or ions (of an ionic substance in solution)

16. Time rate of changes k: Gas exchange coeff. Zml: mixed layer=40m = ca. 8 days When CO2 enters the ocean, approx. 19 out of 20 molecules react with carbonate to form bicarbonate:

19. = ca. 160 days

20. The (short term) organic carbon cycle The photosynthesis reaction removes carbon atoms from the atmosphere and incorporates them into the living tissue of green plants.  It requires energy derived from radiation in the visible part of the electromagnetic spectrum.  The chemical reaction: CO2 + H2O --> CH2O + O2 The respiration (and decay) reaction undoes the work of photosynthesis, thereby returning carbon atoms to the atmosphere: CH2O + O2 --> CO2 + H2O Oxygenic photosynthesis, oxygen from sea water Also: onoxygenic photosynthesis: H2S instead of H2O Calvin-Benson cycle

21. Organic pump The marine biosphere operates like a 'biological pump'.  In the sunlit uppermost 100 meters of the ocean, photosynthesis serves as a source of oxygen and a sink for carbon dioxide and nutrients like phosphorous.  DIC and [H+] decrease, net consumption of CO2 in the upper layers, has to be balanced by inorganic carbon by transport Sink of CO2

24. The marine biosphere is active only in those limited regions of the ocean where upwelling is bringing up nutrients from below.  Once nutrients reach the sunlit upper layer of the ocean they are used up in a matter of days by explosive plankton blooms. 

25. Deeper layers • Fecal pellets and dying marine organisms decay as they settle into the deeper layers of the ocean, consuming dissolved oxygen and giving off (dissolved) carbon dioxide.  • Hence, these layers have much higher carbon dioxide concentrations and lower oxygen concentrations than the waters just below the surface. 

26. The Marine Carbonate System • Carbon dioxide: enters the ocean from atmosphere; steady exchange at surface • Solubility: in water is low! But CO2 reacts with water to form ions: carbonate (CO32-) and bicarbonate (HCO3-) • Most of marine CO2 is stored as bicarbonate. Therefore, CO2 is never limiting photosynthesis in seawater, but it is in freshwater (low pH prevents bicarbonate) • Respiration: CO2 is added, reacts with water:H2O + CO2 = HCO3- + H+; [H+] rises, which means pH sinks! • Primary production: CO2 is removed, HCO3- converts to free CO2 to keep the chemical balance; [H+] falls, which means pH rises! • Soft tissue (weiches Gewebe)

27. Examples:

30. Hard parts

31. Example for Hard parts: Calcification: calcareous shells or skeletons

32. Calcification: Some marine organisms combine calciumwith bicarbonate ions to make calcareous shells or skeletons CO2 balance of calcification: Calcification produces CO2 !Ca2+ + 2 HCO3-  =  CaCO3 + H2O + CO2 Oceanic blooms of coccolithophorids and production of coral reefs DO NOT help decreasing the atmospheric increase in CO2

33. Dissolution of mineral calcite (and aragonite): Mineral calcium carbonate shells Shells sink and eventually dissolve, either in the water column or in the sediments

34. In contrast, calcium carbonate production and its transport to depth, referred to as the carbonate pump, releases CO2  in the surface layer. Photosynthetic carbon fixation and the flux of organic matter to depth, termed organic carbon pump, generates a CO2  sink in the ocean.

35. Biological Pump(s) The ocean plays a major role in the global carbon cycle, exchanging CO2  with the overlying atmosphere. Uptake of atmospheric CO2  by the oceans is driven by physicochemical processes as well as biological fixation of inorganic carbon species. The biogenic production of organic material and carbonate minerals in the surface ocean and their subsequent transport to depth are termed the "biological carbon pumps".

36. Present/future CO2 increase Increase in atmospheric CO2  concentrations is observed, which inevitably changes the seawater carbonate chemistry when more CO2  is taken up by the surface ocean. If CO2  concentrations keep rising at the present rate, it is expected that surface ocean CO2  concentrations will have increased to 3-fold relative to preindustrial values by the end of this century. This would cause carbonate concentrations and pH to drop by ca. 50 % and 0.35 units, respectively.

37. Equilibrium relationships between these species: pCO2:Partial pressure atm. [ ]:Concentrations/activities pH= - log10 [H+]

39. CO32- 300 240 180 120 60 0

40. The long term organic carbon cycle • Only a tiny fraction of the organic material that is generated by photosynthesis each year escapes the decay process by being buried and ultimately incorporated into fossil fuel deposits or sediments containing more dilute fragments of organic material.  • Through this slow process, carbon from both terrestrial and marine biosphere reservoirs enters into the long term organic carbon cycle.  The rate is so slow as to be virtually unmeasurable.  • Weathering releases carbon back into the other reservoirs.

47. End