Carbonates and oceans

Figure 1 Model simulations of long-term ocean pH changes, averaged horizontally, as a result of atmospheric CO2 emissions shown in the top panel. Reprinted from Caldeira K and Wickett ME (2003) Anthropogenic carbon and ocean pH. Nature 425 365.

Caldeira K and Wickett ME (2003) Anthropogenic carbon and ocean pH. Nature 425 365. 

Oxygen is the most abundant element on earth The earths crust is rich in carbonate and sili cate rocks the oceans are almost entirely water and oxygen constitutes almost one fifth of the air we breathe Carbon ranks only fourteenth among the elements in natural abundance but trails only hydro gen and oxygen in its abundance in the human body It IS the chemical properties of carbon that make it uniquely suitable as the raw material forthe building blocks of life Let s find out more about those chemi cal properties... 

In an oversimplified way, it may be stated that acids of the volcanoes have reacted with the bases of the rocks the compositions of the ocean (which is at the fkst end pokit (pH = 8) of the titration of a strong acid with a carbonate) and the atmosphere (which with its 2 = 10 atm atm is nearly ki equdibrium with the ocean) reflect the proton balance of reaction 1. Oxidation and reduction are accompanied by proton release and proton consumption, respectively. In order to maintain charge balance, the production of electrons, e, must eventually be balanced by the production of. The redox potential of the steady-state system is given by the partial pressure of oxygen (0.2 atm). Furthermore, the dissolution of rocks and the precipitation of minerals are accompanied by consumption and release, respectively. 

The sensitivity of the ocean s chemical role in climate is yet to be fully explored as development of models for the carbon and biological components of oceanic... 

Owing to the stability of the uranyl carbonate complex, uranium is universally present in seawater at an average concentration of ca. 3.2/rgL with a daughter/parent activity ratio U) of 1.14. " In particulate matter and bottom sediments that are roughly 1 x 10 " years old, the ratio should approach unity (secular equilibrium). The principal source of dissolved uranium to the ocean is from physicochemical weathering on the continents and subsequent transport by rivers. Potentially significant oceanic U sinks include anoxic basins, organic rich sediments, phosphorites and oceanic basalts, metalliferous sediments, carbonate sediments, and saltwater marshes. " ... 

Human interaction with the global cycle is most evident in the movement of the element carbon. The burning of biomass, coal, oil, and natural gas to generate heat and electricity has released carbon to the atmosphere and oceans in the forms of CO2 and carbonate. Because of the relatively slow... 

Under low-dose conditions, forest ecosystems act as sinks for atmospheric pollutants and in some instances as sources. As indicated in Chapter 7, the atmosphere, lithosphere, and oceans are involved in cycling carbon, nitrogen, oxygen, sulfur, and other elements through each subsystem with different time scales. Under low-dose conditions, forest and other biomass systems have been utilizing chemical compounds present in the atmosphere and releasing others to the atmosphere for thousands of years. Industrialization has increased the concentrations of NO2, SO2, and CO2 in the "clean background" atmosphere, and certain types of interactions with forest systems can be defined. 

Sodium, 22 700 ppm (2.27%) is the seventh most abundant element in crustal rocks and the fifth most abundant metal, after Al, Fe, Ca and Mg. Potassium (18 400 ppm) is the next most abundant element after sodium. Vast deposits of both Na and K salts occur in relatively pure form on all continents as a result of evaporation of ancient seas, and this process still continues today in the Great Salt Lake (Utah), the Dead Sea and elsewhere. Sodium occurs as rock-salt (NaCl) and as the carbonate (trona), nitrate (saltpetre), sulfate (mirabilite), borate (borax, kemite), etc. Potassium occurs principally as the simple chloride (sylvite), as the double chloride KCl.MgCl2.6H2O (camallite) and the anhydrous sulfate K2Mg2(S04)3 (langbeinite). There are also unlimited supplies of NaCl in natural brines and oceanic waters ( 30kgm ). Thus, it has been calculated that rock-salt equivalent to the NaCl in the oceans of the world would occupy... 

Straight-chain detergents don t work in hard water. Phosphates were added to detergents to soften the water, but phosphates are excellent fertilizer for algae in rivers and oceans. The algae blooms deplete the oxygen in the water, which in turn kills fish. Phosphates were replaced with other water softeners such as sodium carbonate and EDTA. 

Molecules am act one another. Fiuni that simple fact spring fundamentally important consequences. Rivers, lakes, and oceans exist because water molecules attract one another and form a liquid. Without that liquid, there would be no life. Without forces between molecules, our flesh would drip off our bones and the oceans would be gas. Less dramatically, the forces between molecules govern the physical properties of bulk matter and help to account for the differences in the substances around us. They explain why carbon dioxide is a gas that we exhale, why wood is a solid that we can stand on, and why ice floats on water. At very close range, molecules also repel one another. When pressed together, molecules resist further compression. 

The most important type of mixed solution is a buffer, a solution in which the pH resists change when small amounts of strong acids or bases are added. Buffers are used to calibrate pH meters, to culture bacteria, and to control the pH of solutions in which chemical reactions are taking place. They are also administered intravenously to hospital patients. Human blood plasma is buffered to pH = 7.4 the ocean is buffered to about pH = 8.4 by a complex buffering process that depends on the presence of hydrogen carbonates and silicates. A buffer consists of an aqueous solution of a weak acid and its conjugate base supplied as a salt, or a weak base and its conjugate acid supplied as a salt. Examples are a solution of acetic acid and sodium acetate and a solution of ammonia and ammonium chloride. 

Figure 1. Changes in global climate due to increased atmospheric CO2 will alter carbon cycle processes in land, continent margins, and oceans, which will in turn effect the atmospheric C02concentration. Processes that may have effects large enough to Eilter future projections of atmospheric CO2 are listed under their geographic region.

Fan, S., Gloor, M., Mahlman, J., Pacala, S., Sarmiento, ]., Takahashi, T., and Tans, P. (1998). A large terrestrial carbon sink in North America implied by atmospheric and oceanic carbon dioxide data and models. Science 282, 442-446. 

The cycles of carbon and the other main plant nutrients are coupled in a fundamental way by the involvement of these elements in photosynthetic assimilation and plant growth. Redfield (1934) and several others have shown that there are approximately constant proportions of C, N, S, and P in marine plankton and land plants ("Redfield ratios") see Chapter 10. This implies that the exchange flux of one of these elements between the biota reservoir and the atmosphere - or ocean - must be strongly influenced by the flux of the others. 

Rainwater and snowmelt water are primary factors determining the very nature of the terrestrial carbon cycle, with photosynthesis acting as the primary exchange mechanism from the atmosphere. Bicarbonate is the most prevalent ion in natural surface waters (rivers and lakes), which are extremely important in the carbon cycle, accoxmting for 90% of the carbon flux between the land surface and oceans (Holmen, Chapter 11). In addition, bicarbonate is a major component of soil water and a contributor to its natural acid-base balance. The carbonate equilibrium controls the pH of most natural waters, and high concentrations of bicarbonate provide a pH buffer in many systems. Other acid-base reactions (discussed in Chapter 16), particularly in the atmosphere, also influence pH (in both natural and polluted systems) but are generally less important than the carbonate system on a global basis. 

The organic carbon (and thus the organic matter) in seawater is predominantly in dissolved form (DOC) with an average for the whole ocean being 97%. In general, surface ocean concentrations are about 80/ M and decrease to about 40 /iM below 500 m (Peltzer and Hayward, 1996 Hansell and Peltzer, 1998). 

Platt, T. and Harrison, W. G. (1985). Biogenic fluxes of carbon and oxygen in the ocean. Nature 318,55-58. 

The subsequent fate of the assimilated carbon depends on which biomass constituent the atom enters. Leaves, twigs, and the like enter litterfall, and decompose and recycle the carbon to the atmosphere within a few years, whereas carbon in stemwood has a turnover time counted in decades. In a steady-state ecosystem the net primary production is balanced by the total heterotrophic respiration plus other outputs. Non-respiratory outputs to be considered are fires and transport of organic material to the oceans. Fires mobilize about 5 Pg C/yr (Baes et ai, 1976 Crutzen and Andreae, 1990), most of which is converted to CO2. Since bacterial het-erotrophs are unable to oxidize elemental carbon, the production rate of pyroligneous graphite, a product of incomplete combustion (like forest fires), is an interesting quantity to assess. The inability of the biota to degrade elemental carbon puts carbon into a reservoir that is effectively isolated from the atmosphere and oceans. Seiler and Crutzen (1980) estimate the production rate of graphite to be 1 Pg C/yr. 

Broecker, W. S. (1973). Factors controlling CO2 content in the oceans and atmosphere. In "Carbon and the Biosphere" (G. M. Woodwell and E. V. Pecan, eds), pp. 32-50. United States Atomic Energy Commission. 

Chen, C.-T.A. (1978). Decomposition of calcium carbonate and organic carbon in the deep oceans. Science 201, 735-736. 

Revelle, R. and Suess, H. E. (1957). Carbon dioxide exchange between atmosphere and ocean, and the question of an increase of atmospheric CO2 during the past decades, Tellus 9,18-27. 

Calculated from carbon in ocean biota (3000 Tg) and approximate mass ratio for sulfur to carbon of 1 100. 

Van Cappellen, P. and Ingall, E. D. (1994). Benthic phosphorus regeneration, net primary production, and ocean anoxia A model of the coupled marine biogeochemical cycles of carbon and phosphoms. Paleoceanography 9,677-692. 

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