What caused the glacial/interglacial atmospheric pCO2 cycles?

Fifteen years after the discovery of major glacial/interglacial cycles in the CO2 concentration of the atmosphere, it seems that all of the simple mechanisms for lowering pCO(2) have been eliminated. We use a model of ocean and sediment geochemistry, which includes new developments of iron limitation of biological production at the sea surface and anoxic diagenesis and its effect on CaCO3 preservation in the sediments, to evaluate the current proposals for explaining the glacial/interglacial pCO(2) cycles within the context of the ocean carbon cycle. After equilibration with CaCO3 the model is unable to generate glacial pCO(2) by increasing ocean NO3- but predicts that a doubling of ocean H4SiO4 might suffice. However, the model is unable to generate a doubling of ocean H4SiO4 by any reasonable changes in SiO2 weathering or production. Our conclusions force us to challenge one or more of the assumptions at the foundations of chemical oceanography. We can abandon the stability of the Redfield ratio of nitrogen to phosphorus in living marine phytoplankton and the ultimate limitation of marine photosynthesis by phosphorus. We can challenge the idea that the pH of the deep ocean is held relatively invariant by equilibrium with CaCO3. A third possibility, which challenges physical oceanographers, is that diapycnal mixing in ocean circulation models exceeds the rate of mixing in the real ocean, diminishing the model pCO(2) sensitivity to biological carbon uptake.