Aragonite saturation state

P002 =517ppmv. flarag = aragonIte saturation state. See Eq. 15.8 for a definition of fl. Source After Gulnotte, J. M., et al. (2003). Coral Reefs 22, 551-558. (See companion website for color version.)... 

Figure 6.10. Aragonite saturation state versus DIC (dissolved inorganic carbon = SCO2) in Checker Reef porewaters (lower points) as opposed to overlying seawater (upper points). (After Tribble, 1990.)...

Figure 8, A detailed profile of calcite and aragonite saturation states and sediment marker depth in the Northwestern Atlantic Ocean, (Percentages are estimates of the amount of calcite dissolution which must occur to produce a given marker level.)...

The saturation state of aragonite (Fig. 24.5), on the other hand, is affected little by temperature. Aragonite remains supersaturated by a factor of about ten (one log unit) over the gamut of analyses. The supersaturation probably arises from the effect of orthophosphate, present at concentrations of about 100 mg kg-1 in Mono Lake water orthophosphate is observed in the laboratory (Bischoff et al., 1993) to inhibit the precipitation of calcite and aragonite. 

The saturation state of seawater can be used to predict whether detrital calcite and aragonite are thermodynamically favored to survive the trip to the seafloor and accumulate in surfece sediments. Any PIC or sedimentary calcium carbonate exposed to undersaturated waters should spontaneously dissolve. Conversely, PIC and sedimentary calcium carbonate in contact with saturated or supersaturated waters will not spontaneously dissolve. Typical vertical trends in the degree of saturation of seawater with respect to calcite and aragonite are shown in Figure 15.11 for two sites, one... 

Saturation state of seawater, Cl, with respeot to (a) calcite and (b) aragonite as a function of depth. The dashed vertical line marks the saturation horizon. North Pacific profile is from 27.5°N 179.0°E (July 1993) and North Atlantio profile is from 24.5°N 66.0°W (August 1982) from CDIAC/WOCE database http //cdiac.esd.oml.gov/oceans/CDIACmap.html) Section P14N, Stn 70 and Section A05, Stn 84. Source From Zeebe, R.E. and D. Wolf-Gladrow (2001) Elsevier Oceanography Series, 65, Elsevier, p. 26. 

The applicability of scanning Auger spectroscopy to the analysis of carbonate mineral surface reactions was demonstrated by Mucci and Morse (1985), who carried out an investigation of Mg2+ adsorption on calcite, aragonite, magnesite, and dolomite surfaces from synthetic seawater at two saturation states. Results are summarized in Table 2.5. 

Aragonite is the only one of the four carbonate minerals examined that does not have a calcite-type rhombohedral crystal structure. For all the minerals examined, with the exception of aragonite, the two solution saturation states studied represent supersaturated conditions, because at a saturation state of 1.2 with respect to calcite, the seawater solution is undersaturated (0.8) with respect to aragonite. 

At the higher saturation state, the seawater solution is more than 5 times supersaturated with respect to aragonite so that aragonite would be expected to precipitate on the aragonite seed crystal. Results indicated that Mg2+ is adsorbed between 25 to 40 times less on aragonite than on calcite from solutions supersaturated with respect to both minerals. 

It should be kept in mind that, in spite of these major variations in the CO2-carbonic acid system, virtually all surface seawater is supersaturated with respect to calcite and aragonite. However, variations in the composition of surface waters can have a major influence on the depth at which deep seawater becomes undersaturated with respect to these minerals. The CO2 content of the water is the primary factor controlling its initial saturation state. The productivity and temperature of surface seawater also play major roles, in determining the types and amounts of biogenic carbonates that are produced. Later it will be shown that there is a definite relation between the saturation state of deep seawater, the rain rate of biogenic material and the accumulation of calcium carbonate in deep sea sediments. 

A reason that there has been so much controversy associated with the relation between the extent of carbonate dissolution occurring in deep sea sediments and the saturation state of the overlying water is that models for the processes controlling carbonate deposition depend strongly on this relation. Hypotheses have ranged from a nearly "thermodynamic" ocean where the CCD and ACD are close to coincident with calcite and aragonite saturation levels (e.g., Turekian, 1964 Li et... 

Figure 6.4. Histograms of the number of samples found within different ranges of saturation state with respect to aragonite for different shallow water calcium carbonate-rich sediments. Values for Bermuda, Florida Bay and the Everglades were calculated from the data of Berner (1966). (After Morse et al., 1985.)...

However, there is a strong tendency to higher supersaturations with respect to aragonite in the Bahamian sediments, and lower saturation states in the south Florida sediments. Because aragonite is generally the dominate carbonate phase in these sediments, control of the IAP by the most abundant phase does not generally explain these observations. 

Figure 6.11. A. Saturation state of seawater with respect to aragonite as a function of sulfate reduction. Based on general model of Ben-Yaakov (1973), updated by using pK a values and total ion activity coefficients of Millero (1982). B. Observed saturation state of Mangrove Lake, Bermuda pore waters with respect to calcite.

Figure 6.12. Calculated saturation states with respect to aragonite of marine pore waters undergoing anoxic diagenesis as a function of the original C/N ratio of labile organic matter. The extent of diagenesis is represented by the organic C oxidized in the sediment-pore water system, shown as inorganic carbon added to pore waters.

Let us now consider the problem from the standpoint of calcite precipitation kinetics. At saturation states encountered in most natural waters, the calcite reaction rate is controlled by surface reaction kinetics, not diffusion. In a relatively chemically pure system the rate of precipitation can be approximated by a third order reaction with respect to disequilibrium [( 2-l)3, see Chapter 2]. This high order means that the change in reaction rate is not simply proportional to the extent of disequilibrium. For example, if a water is initially in equilibrium with aragonite ( 2c=1.5) when it enters a rock body, and is close to equilibrium with respect to calcite ( 2C = 1.01), when it exits, the difference in precipitation rates between the two points will be over a factor of 100,000 The extent of cement or porosity formation across the length of the carbonate rock body will directly reflect these... 

It can be seen that in the region of Devonshire Marsh, located near the thickest part of the freshwater lens (Figure 7.27), that the waters are subsaturated with respect to calcite and aragonite and have high CO2 pressures, apparently derived from organic matter oxidation in the marsh area. The waters have low salinities, low Sr2+ concentrations, and little Mg2+ and Ca2+ derived from dissolution of carbonate rock minerals. Toward the south shore of Bermuda and eastward from Devonshire Marsh, the salinity of the waters increases, and the saturation state approaches near-equilibrium with calcite, and supersaturation with respect to aragonite. Lower Pc02 values characterize the waters farther away from Devonshire Marsh. 

The saturation state of deep seawater with respect to calcite and aragonite on a large scale needs to be determined within an order of magnitude more accuracy than it is now known. 

In order to understand the chemistry of calcium carbonate accumulation in the deep oceans, the sources of calcium carbonate, its distribution in recent pelagic sediments, the saturation state of seawater overlying deep-ocean sediments with respect to calcite and aragonite, and the relation between saturation state and dissolution rate must be known. These aspects of calcium carbonate chemistry are examined in this paper. 

The Geochemical Ocean Section Program (GEOSECS) has produced data from which it is possible to profile the saturation state of seawater with respect to calcite and aragonite in the Atlantic and Pacific oceans. Representative north-south calcite saturation profiles for the Western Atlantic and Central Pacific oceans are presented in Figures 5 and 6 (based on 39). It was observed that the saturation state of seawater with respect to calcite at the CCD was close to constant ( 2 = 0.70 I" 0,05) except in the southern extremes (39). Broecker and Takahashi (31) have recently found that the carbonate ion concentration is close to constant at the FL, when appropriate corrections are made for pressure. The saturation state of seawater at the FL, calculated by the method presented in this paper, is 0.80 0.05. Berger (40) has presented profiles for Rq, FL, CCD and CSL (calcite saturation level) in the eastern and western Atlantic ocean (see... 

Figure 7). His results indicate that Rq and CSL are close to coincident with the probable uncertainty of their determination. A detailed profile showing the relations among the sediment marker levels and the saturation state of seawater with respect to calcite and aragonite in the Northwest Atlantic Ocean is presented in Figure 8.

Calcium carbonate is accumulating in deep ocean sediments, in which the overlying water is undersaturated with respect to both aragonite and calcite, and sediment marker levels closely correspond to unique saturation states. This indicates that dissolution kinetics play an important role in determining the relation between seawater chemistry and calcium carbonate accumulation in deep ocean basins. It is, therefore, necessary to have knowledge of the dissolution kinetics of calcium carbonate in seawater if the accumulation of calcium carbonate is to be understood. 

Figure 4 The saturation state with respect to aragonite versus the extent of sulfate reduction for a closed system containing seawater (after Morse and Mackenzie, 1990).

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