Enamel carbonate apatite

Bone and teeth in mammals and bony fishes all rely on calcium phosphates in the form of hydroxyapatite [Ca5(P04)30H]2, usually associated with around 5% carbonate (and referred to as carbonated apatite). The bones of the endoskeleton and the dentin and enamel of teeth have a high mineral content of carbonated apatite, and represent an extraordinary variety of structures with physical and mechanical properties exquisitely adapted to their particular function in the tissue where they are produced. We begin by discussing the formation of bone and then examine the biomineralization process leading to the hardest mineralized tissue known, the enamel of mammalian teeth. 

The nature of mineral phases present in bone, dentin, enamel and other phosphatic tissues, and their mode of formation have been subjects of lively discussions among health scientists and crystallographers. Bioscientists most commonly accept the viewpoint that the inorganic phase of bones or teeth is principally hydroxyapatite, Caio(P04)6(OH)2, and deviation in Ca/P ratio from common hydroxyapatite (Ca/P = 1.667) observed in mineralized tissues is explained by the presence of amorphous phosphates. In contrast, many crystallographers favor the idea of carbonate apatite, i.e. dahllite, as the major crystalline phase in biophosphates and they doubt the existence of amorphous phases. The topic has been reviewed14,15,22,28, 37,44,47,348-358) no common consent has yet been reached. In the following an attempt is made to at least coordinate the controversial findings. 

Indeed, in the light of current mineralogical theory (McConnell, 1973a) pertaining to carbonate apatites, there is no need to search for either a precursor or any other solid phase in bone — either crystalline or noncrystalline. The chemical composition is indicated for the principal constituents of bovine (dry, fat-free) bone, compared with dental enamel and dentin (Table 3.1.7). When converted to oxides, these values for bone become ... 

Comparison of Enamel and Dentine to DahHite. Infrared spectrophotometry and X-ray diffraction studies of natural apatites before and after thermal treatment, led Herman and Dallemagne (1963) to conclude that among the apatites they studied, francolite and quercyite are comparable and the results were explained by considering that CO3 groups are present within the apatitic lattice by substitution for P04" groups. Dahllite and Curasao carbonate-apatite contain calcite, but no evidence was found for the presence of calcite in francolite and quercyite. Enamel, dentine, and bone were found to be comparable to dahllite (Fig. 19.11). Spectra of... 

Fig. 19.11. Infrared spectra of calcite, dahllite, Curasao carbonate-apatite, enamel (email), and francolite before and after heating at 9(X)°C. (Herman and Dallemagne, 1963.)...

In their publication, LeGeros and LeGeros (1993) oudine the different apatites, ranging from natural apatite (minerals) to biological (human dentin, enamel, and bone) and synthetic (chemically synthesized) apatite. This publication clearly shows that apatite is a group of crystalline compounds. The most important of these compounds is calcium hydroxyapatite. All the related crystal structures, such as fluoroapatite, chloroapatite, and carbonate apatite are derived from it. 

Scientifically speaking, biological apatites, such as apatite crystals of human dentin, enamel, and bone must be classified as carbonate apatites. These substances also demonstrate different levels of solubility because of their various degrees of crystallinity. Therefore, enarnel carbonate apatite is... 

Budz, J. A., Lore, M., and Nancollas, G. H. 1987. Hydroxyapatite and carbonated apatite as models for the dissolution behaviour of human dental enamel. Advances in Dental Research 1 314-21. 

Willamson, B.E. (1982) Low-temperature laser Raman spectroscopy of synthetic carbonated apatites and dental enamel. Aust / Chem., 35,... 

The properties described above have important consequences for the way in which these skeletal tissues are subsequently preserved, and hence their usefulness or otherwise as recorders of dietary signals. Several points from the discussion above are relevant here. It is useful to ask what are the most important mechanisms or routes for change in buried bones and teeth One could divide these processes into those with simple addition of new non-apatitic material (various minerals such as pyrites, silicates and simple carbonates) in pores and spaces (Hassan and Ortner 1977), and those related to change within the apatite crystals, usually in the form of recrystallization and crystal growth. The first kind of process has severe implications for alteration of bone and dentine, partly because they are porous materials with high surface area initially and because the approximately 20-30% by volume occupied by collagen is subsequently lost by hydrolysis and/or consumption by bacteria and the void filled by new minerals. Enamel is much denser and contains no pores or Haversian canals and there is very, little organic material to lose and replace with extraneous material. Cracks are the only interstices available for deposition of material. 

One further difference between the tissues should be noted briefly—that of turnover—which holds implications for the nature of the isotopic signal recorded and its interpretation. Bone is constantly resorbed and reformed during life, i.e., it turns over , whereas enamel and dentine do not, although secondary dentine can be later accreted. Enamel and dentine form during a discrete period in the individual s life. This means that carbon isotope dietary signals in bone, for both collagen and apatite, reflect diet integrated over years, whereas those in enamel and dentine increments reflect diet at time of formation. 

For Klasies, although most values for both enamel and bone apatite fall within one standard deviation of the mean of (corrected) modem browser values (Fig. 5.5), some bone specimens fall outside this range. These enriched specimens suggest that a limited degree of equilibration with matrix carbonates has taken place, although inclusion of a limited amount of Q grass in the diet is a plausible alternative explanation for UCT 1025, Raphicerus sp. which as noted above could be the more opportunistic species, Raphicerus campestris. 

In the million year range, however, there is clearer evidence for isotopic alteration which also apparently increases with age. Unfortunately, at present there are few reliable browser and grazer data beyond the Late Pleistocene, i.e., in the Middle Pleistocene, which would allow determination of the periods during which bone apatite and enamel begin to deviate. The indications are that the timing should be different. Material from the site of Florisbad falls within the late Middle Pleistocene ( 125-200 Ka), but at present carbon isotope data are only available for three species of uncertain and/or opportunistic diets (Brink and Lee-Thorp 1992), so that extent or direction of isotopic alteration is impossible to separate from dietary vagaries. 

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