Hydroxyapatite calcium phosphate precipitation

Tricalcium phosphate, Ca2(P0 2> is formed under high temperatures and is unstable toward reaction with moisture below 100°C. The high temperature mineral whidockite [64418-26-4] although often described as P-tricalcium phosphate, is not pure. Whidockite contains small amounts of iron and magnesium. Commercial tricalcium phosphate prepared by the reaction of phosphoric acid and a hydrated lime slurry consists of amorphous or poody crystalline basic calcium phosphates close to the hydroxyapatite composition and has a Ca/P ratio of approximately 3 2. Because this mole ratio can vary widely (1.3—2.0), free lime, calcium hydroxide, and dicalcium phosphate may be present in variable proportion. The highly insoluble basic calcium phosphates precipitate as fine particles, mosdy less than a few micrometers in diameter. The surface area of precipitated hydroxyapatite is approximately... 

Sodium carboxymethyl chitin and phosphoryl chitin had most evident influences on the crystallization of calcium phosphate from supersaturated solutions. They potently inhibited the growth of hydroxyapatite and retarded the rate of spontaneous calcium phosphate precipitation. These chitin derivatives were incorporated into the precipitate and influenced both the phase and morphology of the calcium phosphate formed (flaky precipitate resembling octacalcium phosphate instead of spherical clusters in the absence of polysaccharide) [175]. 

Calcium phosphate precipitation may also be involved in the fixation of phosphate fertilizer in soils. Studies of the uptake of phosphate on calcium carbonate surfaces at low phosphate concentrations typical of those in soils, reveal that the threshold concentration for the precipitation of the calcium phosphate phases from solution is considerably increased in the pH range 8.5 -9.0 (3). It was concluded that the presence of carbonate ion from the calcite inhibits the nucleation of calcium phosphate phases under these conditions. A recent study of the seeded crystal growth of calcite from metastable supersaturated solutions of calcium carbonate, has shown that the presence of orthophosphate ion at a concentration as low as 10-6 mol L" and a pH of 8.5 has a remarkable inhibiting influence on the rate of crystallization (4). A seeded growth study of the influence of carbonate on hydroxyapatite crystallization has also shown an appreciable inhibiting influence of carbonate ion.(5). 

The insoluble Ca(II) salts of weak acids, such as calcium phosphate, carbonate, and oxalate, serve as the hard structural material in bone, dentine, enamel, shells, etc. About 99% of the calcium found in the human body appears in mineral form in the bones and teeth. Calcium accounts for approximately 2% of body weight (18,19). The mineral in bones and teeth is mosdy hydroxyapatite [1306-06-5] having unit cell composition Ca10(PO4)6(OH)2. The mineralization process in bone follows prior protein matrix formation. A calcium pumping mechanism raises the concentrations of Ca(II) and phosphate within bone cells to the level of supersaturation. Granules of amorphous calcium phosphate precipitate and are released to the outside of the bone cell. There the amorphous calcium phosphate, which may make up as much as 30—40% of the mineral in adult bone, is recrystallized to crystallites of hydroxyapatite preferentially at bone collagen sites. These small crystallites do not exceed 10 nm in diameter (20). 

In general, saliva (as well as plaque fluid) is supersaturated with respect to calcium-phosphate salts, and they prevent tendency to dissolve mineral crystals of teeth. Moreover, precipitation of calcium-phosphate salts that include hydroxyapatite may also occur (remineralization) in early lesions of tooth surfaces injured by acidic bacterial products (i.e., lactic acid). Salivary fluoride facilitates calcium-phosphate precipitation, and such crystals (i.e., fluorapatite) show lower acid solubility properties that lead to an increased caries preventive effect. The increase of pFI (i.e., buffer capacity and pH of saliva, as well as ureolysis in dental plaque) also facilitates crystal precipitation and remineralization (4, 13). 

Figure3.33 Calcium phosphate precipitates and theirdiffractionpatterns (a) image and(b) diffraction pattern of octacalcium phosphate crystal (c) image and (d) diffraction pattern of hydroxyapatite crystal. R, R2 are vectors.

Brown JL (1981) Calcium phosphate precipitation Effects of common and foreign ions on hydroxyapatite crystal growth. Soil Sci Soc J 45 482-486 Bulka GR, Vinokurov VM, Nizamutdinov NM, Hasanova NM (1980) Dissymmetrization of crystals Theory and experiment. Phys Chem Minerals 6 283-293 Bums RG (1970) Mineralogical Applications of Crystal Field Theory. Cambridge University Press, Cambridge... 

Damen and Ten Cate [98] studied calcium phosphate precipitation with and without the presence of silicic acid and showed that polysilicic acid, not monomer, acted as a substrate for hydroxyapatite nucleation, caused a 60% reduction in the induction period in seeded reactions and overcame part of the inhibitory effect of phosprotein. In all cases hydroxyapatite grew in the presence of silica even when the system was seeded with a different polymorph of calcium phosphate. It was concluded that silica promotes dental calculus formation. 

Hydroxyapatite, Ca2Q(PO (OH)2, may be regarded as the parent member of a whole series of stmcturaHy related calcium phosphates that can be represented by the formula M2q(ZO X2, where M is a metal or H O" Z is P, As, Si, Ga, S, or Cr and X is OH, F, Cl, Br, 1/2 CO, etc. The apatite compounds all exhibit the same type of hexagonal crystal stmcture. Included are a series of naturally occurring minerals, synthetic salts, and precipitated hydroxyapatites. Highly substituted apatites such as FrancoHte, Ca2Q(PO (C02) (F,0H)2, are the principal component of phosphate rock used for the production of both wet-process and furnace-process phosphoric acid. 

Tricalcium Phosphate. Commercial tricalcium phosphate (TCP) is actually an amorphous basic calcium phosphate close to hydroxyapatite in composition. Because of its extremely low solubiUty in water, TCP is precipitated almost quantitatively from dilute phosphate solutions with a slurry of hydrated lime. TCP is separated by dmm-, spray-, or flash-drying the TCP slurry, with or without intermediate sedimentation or filtration steps. It is used as an industrial-grade flow conditioner and parting agent. 

NOTE Depending on operating conditions, alkalinity, pH level, point of feed, and so forth, when phosphate is present in the BW, calcium salts precipitate primarily as either insoluble tricalcium phosphate [Ca3(P04)2] or hydroxyapatite [Ca]0(0H)2(P04)6J. 

Some phosphate-cycle reactions are shown below, and, although for the sake of simplicity only calcium phosphate is shown as a precipitant, depending on the operational circumstances, the reaction produces either tricalcium phosphate, hydroxyapatite, or a combination of both salts. 

NOTE If the BW contains phosphate, the preferred reaction is for calcium to precipitate as hydroxyapatite, rather than to chelate with EDTA or NTA (a further competing anion effect). Consequently, there would seem to be no valid reason to produce combined phosphate-chelant programs, with the chelant acting as a reserve against unforeseen hardness incursions caused by a softener leakage, or other source. In practice, the chelant acts to solubilize existing deposits, producing a very clean boiler. 

Chitosan scaffolds were reinforced with beta-tricalciiun phosphate and calcium phosphate invert glass [177]. Along the same line, composites of Loligo beta-chitin with octacalcium phosphate or hydroxyapatite were prepared by precipitation of the mineral into a chitin scaffold by means of a double diffusion system. The octacalciiun phosphate crystals with the usual form of 001 blades grew inside chitin layers preferentially oriented with the 100 faces parallel to the surface of the squid pen and were more stable to hy-... 

Precipitation can occur if a water is supersaturated with respect to a solid phase however, if the growth of a thermodynamically stable phase is slow, a metastable phase may form. Disordered, amorphous phases such as ferric hydroxide, aluminum hydroxide, and allophane are thermodynamically unstable with respect to crystalline phases nonetheless, these disordered phases are frequently found in nature. The rates of crystallization of these phases are strongly controlled by the presence of adsorbed ions on the surfaces of precipitates (99). Zawacki et al. (Chapter 32) present evidence that adsorption of alkaline earth ions greatly influences the formation and growth of calcium phosphates. While hydroxyapatite was the thermodynamically stable phase under the conditions studied by these authors, it is shown that several different metastable phases may form, depending upon the degree of supersaturation and the initiating surface phase. 

Despite the importance of the precipitation of calcium phosphates, there is still considerable uncertainty as to the nature of the phases formed in the early stages of the precipitation reactions under differing conditions of supersaturation, pH, and temperature. Although thermodynamic considerations yield the driving force for the precipitation, the course of the reaction is frequently mediated by kinetic factors. Whether dicalcium phosphate dihydrate (CaHPO HoO, DCPD), octacalcium phosphate (Ca HfPO, 2.5 H20, OCP), hydroxyapatite (Cag (PO fOH), HAP), amorphous calcium phosphate (ACP), or a defect apatite form from aqueous solution depends both upon the driving force for the precipitation and upon the initiating surface phase. Thermodynamically, the relative supersaturation, o, is given by... 

Hydroxyapatite (with some carbonate inclusions) is the most stable of the possible calcium phosphate salts that can be formed under physiological conditions. However, it is not the most rapid one to form. Instead, octacalcium phosphate (OCP) will precipitate more readily than hydroxyapatite. This led Brown in 1987 to propose that, as the kinetically favoured compound, OCP precipitates first, and then undergoes irreversible hydrolysis to a transition product OCP hydrolyzate [68]. This hypothesis is consistent with the observation that enamel comprises hydroxyapatite crystals that have the long, plate-like morphology that is generally considered characteristic of OCP crystals [69]. Overall, it seems that enamel crystals, with their elongated form, result from early precipitation of OCP, which forms a template on which hydroxyapatite units grow epitaxially [70,71]. This leads to enamel mineralisation with the observed thin, ribbon-like structure of crystals. 

The primary purpose of phosphate addition is to precipitate the hardness constituents. The calcium reacts with phosphate under the proper pH conditions to precipitate calcium phosphate as calcium hydroxyapatite, Cain(P04)fi(0H)2. This is a flocculent precipitate that tends to be less adherent to boiler surfaces than simple tricalcium phosphate, which is... 

The presence of phosphate increases the ability of the mitochondria to accumulate Ca2+, partly because of the buffering effect of the phosphate on the pH of the matrix, and partly because of the precipitation of insoluble calcium phosphate within the matrix. The formation of insoluble calcium phosphate lowers the internal free [Ca2+] and favours further influx. The amorphous nature of the precipitate is of interest as the formation of crystalline hydroxyapatite would be expected. Mitochondria must contain a factor that inhibits this process. 

The level of calcium in solution will depend upon the presence of precipitating anions, notably phosphate and carbonate. Calcium will precipitate as the phosphate to give hydroxyapatite, Caio(P04)6(OH)2, in bones and teeth, and as the phosphate or carbonate to give other structures, including small crystals, or non-crystalline deposits in cells. Small crystals of calcium carbonate, found in the inner ear of some animals, are responsible for the control of balance. Various calcified tissues result from the precipitation of calcium salts, such as hydroxyapatite in the calcification of the aortic wall, and the oxalate in various stones. 

Osteocalcin has two high affinity and two or three low affinity sites for calcium. It limits growth of calcium phosphate crystals, and inhibits precipitation of hydroxyapatite. This cannot be achieved by the decarboxylated protein. Calcified tissue from various sources also contains gla proteins.459 Gla proteins are not found in invertebrates. 

Calcium phosphate will ordinarily precipitate at concentrations typically exceeding 5 ppm PO4 or less, forming amorphous calcium orthophosphate (tricalcium phosphate) sludge, Ca3(P04>2, in the bulk water and crystalline hydroxyapatite, Caio(OH)2(P04)2, at heat-transfer surfaces. 

As well as being used as a scaffold for tissue engineering, Hutchens et al. [64] described the creation of a calcium-deficient hydroxyapatite, the main mineral component of bone. Calcium phosphate particles were precipitated in BC by consecutive incubation of calcium chloride and sodium phosphate solutions. Initial tests with osteoblasts in the in vitro evaluation showed that solid fusion between the material and the bone tissue is possible. Hence, this material is a good candidate for use as a therapeutic implant to regenerate bone and heal osseous damage. 

Tricalcium Phosphate Precipitated Calcium Phosphate Calcium Hydroxyapatite... 

Fluorine (F) and its metabolites are of importance in protecting teeth from caries. Fluorine is included in calcium hydroxyapatite, and it promotes the precipitation of calcium phosphate Ca(P03)2 and accelerates the remineralization. The necessary concentration of Fluorine added to drinking water to prevent caries is approximately 1 mg/L. Application of higher Fluorine concentrations (above 8 mg/L) leads to fluorosis. This is a disease that is characterized by a disturbance in the function of the thyroid gland. A long-term application of fluorine leads to intensive mineralization (possible precipitation of calcium sulfate), deformation of bones with possible accretion, and calcification of the connections. 

---