Enzyme kinetics

Calcite compensation depth (CCD) is the depth in the oceans below which the rate of supply of calcite (calcium carbonate) lags behind the rate of solvation, such that no calcite is preserved. Aragonite compensation depth (hence ACD) describes the same behaviour in reference to aragonitic carbonates.

Calcium carbonate is essentially insoluble in sea surface waters today. Shells of dead calcareous plankton sinking to deeper waters are practically unaltered until reaching the lysocline where the solubility increases dramatically. By the time the CCD is reached all calcium carbonate has dissolved according to this equation:

$\mathrm{C}\mathrm{a}\mathrm{C}{\mathrm{O}}_{\mathrm{3}}+\mathrm{C}{\mathrm{O}}_{\mathrm{2}}+{\mathrm{H}}_{\mathrm{2}}\mathrm{O}\mathrm{\rightleftharpoons }\mathrm{C}{\mathrm{a}}^{\mathrm{2}+}\mathrm{(}\mathrm{a}\mathrm{q}\mathrm{)}+\mathrm{2}\mathrm{H}\mathrm{C}{O}_{\mathrm{3}}^{\mathrm{-}}\mathrm{(}\mathrm{a}\mathrm{q}\mathrm{)}$

Calcareous plankton and sediment particles can be found in the water column above the CCD. If the sea bed is above the CCD, bottom sediments can consist of calcareous sediments called calcareous ooze which is essentially a type of limestone or chalk. If the exposed sea bed is below the CCD tiny shells of CaCO₃ will dissolve before reaching this level, preventing deposition of carbonate sediment, unless the seabed is above the CCD, for example along a mid-ocean ridge. As the sea floor spreads thermal contraction of the plate may bring the carbonate layer below the CCD; the carbonate layer may be prevented from chemically interacting with the sea water by overlying sediments such as a layer of siliceous ooze or abyssal clay deposited on top of the carbonate layer.

Variations in value of the CCD

The exact value of the CCD depends on the solubility of calcium carbonate which is determined by temperature, pressure and the chemical composition of the water - in particular the amount of dissolved CO₂ in the water. Calcium carbonate is more soluble at lower temperatures and at higher pressures. It is also more soluble if the concentration of dissolved CO₂ is higher. Adding a reactant to the above chemical equation pushes the equilibrium towards the right producing more products: Ca²⁺ and HCO₃^-, and consuming more reactants CO₂ and calcium carbonate according to Le Chatelier's principle.

At the present time the CCD in the Pacific Ocean is about 4200 - 4500 metres except beneath the equatorial upwelling zone, where the CCD is about 5000 m. In the temperate and tropical Atlantic Ocean the CCD is at approximately 5000 m. In the Indian Ocean it is intermediate between the Atlantic and the Pacific. The variation in the depth of the CCD largely results from the length of time since the bottom water has been exposed to the surface; this is called the "age" of the water mass. Consequently the CCD is, on average, deeper in the Atlantic Ocean, shallower in the Pacific Ocean and of intermediate depth in the Indian Ocean. Relative ages of these basins can be inferred from the pattern of ocean currents which form a global conveyor belt. Because organic material, such as fecal pellets from copepods, sink from the surface waters into deeper water, deep water masses tend to accumulate dissolved carbon dioxide as they age. The oldest water masses have the highest concentrations of carbon dioxide and therefore the shallowest CCD. The CCD is relatively shallow in high latitudes with the exception of the North Atlantic and regions of Southern Ocean where downwelling occurs. This downwelling brings young, surface water with relatively low concentrations of carbon dioxide into the deep ocean, depressing the CCD.

In the geological past the depth of the CCD has shown significant variation. In the Cretaceous through to the Eocene the CCD was much shallower globally than it is today; due to intense volcanic activity during this period atmospheric carbon dioxide concentrations were much higher. Higher concentrations of carbon dioxide resulted in a higher partial pressure of carbon dioxide over the ocean. This greater pressure of atmospheric carbon dioxide leads to increased dissolved carbon dioxide in the ocean mixed surface layer. This effect was somewhat moderated by the deep oceans' elevated temperatures during this period. In the late Eocene the transition from a greenhouse to an icehouse Earth coincided with a deepened CCD.

Today, increasing atmospheric concentration of CO₂ from combustion of fossil fuels may elevate the CCD to some degree, with zones of downwelling first being affected.

John Murray investigated and experimented on the dissolution of calcium carbonate and was first to identify the carbonate compensation depth in oceans.

See also

• Ocean acidification
• Lysocline
• Carbonate pump