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REACTIONS OF FLUORIDE ION WITH HYDROXYAPATITE

BY HAROLD G. MCCANN
(From the National Instituteof Dental Research, National Institutes of Health,
Bethesda, Maryland)
(Received for publication, September 22, 1952)

A problem of long standing in the study of dentin and enamel is the


exact nature and structure of the inorganic material in these tissues. A
review of these studies from the time of Berzelius in 1845 up to 1949 has
been published by Armstrong (1). In general the mineral component of

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teeth as well as bones consists chiefly of a basic calcium phosphate which
is most probably hydroxyapatite (2, 3). Hydroxyapatites may be syn-
thesized in the laboratory and their basic chemistry and reactions studied
directly. The use of a synthetic hydroxyapatite instead of the natural
hydroxyapatites, as may be found in teeth and bones, avoids possible
complications introduced by extraneous chemicals present. in the natural
materials. Chemical methods devised to study the synthetic apatites may
then be adapted for study of natural tooth substance. At the same time
information is obtained concerning basic chemical reactions which take
place and the effects of varying conditions on these basic reactions. In
these experiments we have been concerned for obvious reasons (4, 5) pri-
marily with reactions between the fluoride ion and synthetic hydroxyapa-
tite.
EXPERIMENTAL

Preparation of Hydroxyapatite-This study was made on a series of syn-


thesized compounds ranging in empirical composition from Ca9.g(P04)6-
(OH)1 having a Ca:P mole ratio of 1.593 to that corresponding to pure
hydroxyapatite, Calo(PO&(OH)z, having a Ca:P ratio of 1.667. These
hydroxyapatites, listed with their analyses in Table I, were prepared by a
modification of the acidimetric precipitation method of Rathje (6, 7), later
employed by Egan et al. (8).
To 6 liters of continuously boiling solution (approximately 1 M in respect
to an ammonium salt) in a 12 liter flask were added 2 liters each of a
solution of 0.12 M KH2P0, and 0.20 M Ca(NO& at an equal rate of about
60 ml. per hour for 8 hour periods during the day. The slurry was left
boiling overnight and addition continued the following day. Samples K
and I, were allowed to cool overnight and absorbed CO2 as shown in Table
I. The pH was kept, just alkaline to phenolphthalein, brom cresol purple,
or brom phenol blue by the periodic addition of concentrated NH,OH.
247
248 HYDROXYAP4TITE-FLUORIDE ION REACTION

The NH&l first used caused the presence of 0.3 to 0.5 per cent Cl as an
impurity. This was avoided by the use of ammonium nitrate, but am-
monium acetate or borate made it easier to maintain the desired pH. The
final products were filtered on a sintered glass funnel, washed with copious
quantities of distilled water, and dried at 110. All chemicals used were
reagent grade. The Ca(NO& was prepared from CaC03 treated with a
slight excess of HNOS, the COP was boiled off, and the excess HNOJ neu-
tralized.
A hydroxyapatite radioactive in respect to both calcium and phosphorus
was prepared from 10 gm. of CaC03 containing 1.5 mc. of Ca45 and 8.15
gm. of KH2P04 plus 2 ml. of a solution containing 2 mc. of P32as phosphate
in dilute HCl. This sample was analyzed gravimetrically after it had

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decayed for 2; months.

TABLE I
Analyses of Hydroxyapaiites Prepared and Used in This Study

Apatite sample No. CaO PZOS Ratio Cl CO2 Particle size


Ca:P
_ - ~-_____
per cent ger cent ?tSOkS P er ceni rer c&
I 53.32 42.40 1.593 0.35 Some particles 3 to 4 p
K 53.54 41.62 1.628 0.51 0.31 Small; few crystals
1.645 0.39 0.64 Needles; some 6 to 7 p
ii 53.65 41.53
40.83 1.663 Nil Few very small crystals
II 53.10 40.39 1.665 Mostly amorphous; smaller
Radioactive 51.85 40.01 1.641 I
than Sample Q
-
* Microscopical observation

Although these preparations varied considerably in composition, it has


been suggested by Bale et al. (a), Hendricks and Hill (3), and Posner and
Stephenson (9) that all such materials are hydroxyapatite with entrapped
acid phosphate ions on the surfaces.
Treatment of Hydroxyapatites with Fluoride-These apatites were treated
in various ways in order to determine the effect of concentration of the
fluoride ion, temperature, and Ca:P ratio on reactions with the fluoride
ion. Concentration of fluoride, usually as NaF, was varied from 1 part per
million such as occurs naturally in water up to 2 per cent NaF as used in
the topical application of fluoride to the teeth. Temperatures of 20,
37, and 100 were employed.
Samples in the more concentrated solutions were treated by placing 2.5
gm. of the solid apatite into a container and adding 100 ml. of a solution
containing the desired fluoride concentration. At 37 and below, poly-
ethylene bottles were used; at loo, Pyrex flasks. The more dilute solu-
H. G. MCCANN 249

tions were made up in 12 liter flasks, as a volume of 10 liters of solution


was employed to obtain sufficient fluoride to react with 2.5 gm. of apatite.
Smaller amounts were sometimes used when insufficient material was avail-
able; a less complete analysis was then obtained. Samples were boiled
continuously to maintain 100 temperature; at lower temperatures samples
were placed in a constant temperature oven or room and shaken occasion-
ally. After a period of time varying from several days for the 100 samples
to 1 to 4 months for the lower temperature samples, they were filtered,
washed, and dried at 110. The filtrates from the concentrated samples
included the washings and were made up to 500 ml. 1 liter of filtrate from
the dilute solutions was reserved.
Analytical-The original apatites and the treated solids were anilyzed

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gravimetrically for calcium by double precipitation of the oxalate from
acid solution by slow addition of NHIOH to avoid contamination with
phosphate, with final weighing as the fluoride, and for phosphate by double
precipitation as magnesium ammonium phosphate to assure the proper
stoichiometric relationship (10). Fluoride was determined calorimetrically
by visual matching or spectrophotometrically; both methods are modifica-
tions of the Willard and Winter method (11). In the liquid filtrates cal-
cium was determined microvolumetrically on a concentrated aliquot by a
modification of the ceric sulfate procedure of Kirk (12), and phosphorus
spectrophotometrically by the molybdivanadophosphoric acid procedure
as modified by Simonsen et al. (13).
Radioactivity ABeasurements-Counts were made with a thin mica window
Geiger tube and a Nuclear Instrument scaling unit model No. 163. The
mixed Ca4j and P32 were determined in the same sample by the use of an
aluminum absorber according to the method of Comar et al. (14). Samples
of 0.100 gm. were equilibrated with a series of 500 ml. of 1 p.p.m. to 1 per
cent F for 4 days at 20; then they were filtered and aliquots counted.
Electrolytic Conductivity Apparatus-The Wheatstone bridge was made
up of a Campbell-Shackelton shielded ratio box, Leeds and Northrup No.
1553, and a six dial shielded alternating current resistance box from 0.01
to 11,111.l ohms, No. 4764. The 500, 1000, and 2000 cycle oscillator and
amplifier were standard Leeds and Northrup instruments, Nos. 9842 and
9847. A 5 inch DuMont type 274-A oscillograph served as null-point
indicator. Cell capacity was compensated by an adjustable air capacitor,
No. 4914. Leeds and Northrup conductivity cells were employed and
platinized according to the directions of Jones and Bollinger (15). During
measurement, cells were immersed in a constant temperature bath held to
f0.01. Cells were standardized with KC1 solutions by using the specific
conductance values and directions given by Jones and Bollinger (16).
The conductivity of solutions containing 1 to 1000 p.p.m. of fluoride ion
250 HYDROXYAPATITE-FLUORIDE ION REACTION

as NaF mixed with hydroxyapatite Sample II and equilibrated for 4 to 8


days at 37 was measured.

TABLE II
Treatment of Hydroxyapatites with Concentrated Fluoride Solutions
2.5 gm. of hydroxyapatite treated at 37 with 100 ml. of the indicated sodium
fluoride solution.

Original T
solution Solid Filtrate 1 Solid
ApatiE;ample

F idjusted P Ca
Ca:Pt
_
per cent moles PM B xx3 PM

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I (1.593)* 0.09 53.56 42.45 0.10 1.598 1.593 41 22 123 131
0.95 53.60 41.89 0.52 1.620 1.596 250 9 750 690
K (1.628) 0.09 53.70 41.48 0.21 1.639 1.629 94 27 282 270
L (1.645) 0.095 53.77 41.24 0.04 1.651 1.648 16 22 48 46
0.95 54.01 41.08 0.38 1.665 1.647 173 22 519 500
Q (1.663) 0.095 53.89 41.05 0.07 1.662 1.659 20 14 60 92
0.19 53.96 41.08 0.09 1.663 1.659 27 14 81 118
0.475 54.39 40.77 0.39 1.689 1.671 167 23 501 510
0.950 54.60 40.47 0.74 1.708 1.674 323 19 969 970
II (1.665) 0.095 52.96 40.31 0.19 1.663 1.655 40 28 120 250
0.19 52.89 40.19 0.24 1.666 1.655 48 28 144 320
0.95 53.24 39.89 0.80 1.690 1.652 290 42 8701 1,050
1.90 53.36 38.84 1.74 1.739 1.656 833 5 2,499 2,290
11 WWt 0.095 53.10 40.51 0.21 1.660 1.650 51 13 153 280
9.5 57.08 25.4917.4 2.835 1.56 5980 Low 17,940 22,900
II (NH,F)t 0.095 53.20 40.43 0.52 1.666 1.642 142 9 426 680

* The ratio of the original apatite is given in parentheses for convenience in re-
ferring to changes occurring through reaction with fluoride.
f KF and NH,F substituted for NaF used in previous samples. The KF permits
a higher fluoride concentration due to much greater solubility. The increased
reaction with the NH,F is due to its greater acidity.
$ Actual Ca:P ratio adjusted by subtracting the CaO equivalent of the F from
the actual per cent CaO.
5 Actual moles of phosphorus X 3, as approximately 1 mole of P would be released
for each 3 moles of F in a direct replacement reaction. This calculation allows a
ready comparison with the amount of fluoride reacted.

Results
Treatment with Concentrated Fluoride Solutions at 9 (Table II)-The
results of treating the various hydroxyapatite samples with fluoride con-
centrations in and above the range used in topical application to teeth are
shown in Table II. By comparing the analysis of the solid before and
after treatment, together with the concentration of calcium and phospho-
H. G. MCCANN 251

rus released into the liquid phase during reaction, it was possible to deter-
mine in what manner the fluoride had reacted with the solid: by double
decomposition to form CaFz or by exchange with the hydroxyl to form
fluorapatite. If reaction with phosphate occurs somewhat according to
the reaction
(A) Ca&POJc(OHz) + 20F- -+ 1OCaFz + 6P0, + 20H-

the ratio of Ca to P in the solid will be increased, since the calcium will
remain in the solid as CaF2, while the phosphate will be removed into the
solution. If this reaction occurs exclusively, the original ratio will be ob-
tained by adjusting the experimental ratio for the calcium combined
with fluoride. This is the case with Samples I, K, and L, indicating the

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formation of calcium fluoride, and very little or no fluorapatite.
If fluorapatite forms according to the reaction
(B) Calo(POa)6(OH)s + 2F- + Calo(P04)6F2 + 20H-

or hydroxyfluorapatite according to the reaction as suggested by Giesecke


CC) Calo(P04),(OH)~ + F- -+ CadPO&FOH + OH-

and Rathje (17), the Ca: P ratio of the solid remains unchanged, as the hy-
droxyl group is the only portion of the molecule affected. If the ratio is
adjusted to calcium equivalent to fluoride in this case, the ratio will be
lower than that in the original apatite. Samples Q and II give results
indicating considerable fluorapatite formation at fluoride concentrations
up to 0.2 per cent, and probably some fluorapatite along with the CaFz
at higher fluoride concentrations with Sample II.
The calcium and phosphate content of the liquid phase also indicates in
most cases a similar type of reaction. Since the calcium content is low, it
was assumed that if calcium fluoride were formed most of the phosphate in
solution would be due to replacement by fluoride. According to Reaction
A above, 20 fluoride ions replace 6 phosphate ions so that moles of P X 3.33
= moles of F. This gives results which are somewhat high since some of
the phosphate is due to the apatite solubility. However, if moles of P are
multiplied by 3, results are obtained which indicate somewhat quantita-
tively the amount of phosphate replaced, although, when the amount of
fluoride which reacted is low, a greater proportion of the phosphate is due
to apatite solubility.
Treatment with Concentrated Fluoride Solutions at 100 (Table III)-By a
similar calculation it is seen that Sample I has reacted mostly according to
Reaction A as before, but Sample L has reacted t.o form fluorapatite ac-
cording to Reaction B, while Sample K, although forming mostly CaF2,
has reacted partially as in Reaction B.
Dilute and Intermediate Values of Fluoride Concentrations at 37 (Tables
252 HYDROXYAPATITE-FLUORIDE ION REACTION

IIi and 8)-The results of treating the hydroxyapatite samples with the
fluoride concentrations found in natural waters and with intermediate val-
ues up to those used in topical application to teeth are shown in Table IV.
The first four values of the Ca: P ratio in Table IV are somewhat lower
than the original hydroxyapatite due to reaction with the large volume of
water. As the fluoride concentration goes up, this effect is overcome.
However, since the formation of calcium fluoride would increase this ratio
considerably, the assumption that fluorapatite has formed is believed to be
valid. Up through 100 p.p.m. of fluoride, only fluorapatite is formed;
above this, considerable amounts of CaF, are formed. Although the fluo-

TABLE III

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Treatment with Concentrated Fluoride Solutions
2.5 gm. of hydroxyapatite treated at 100 with 100 ml. of the indicated sodium
fluoride concentration.

Original Solid Filtrate Solid


solution
_
F cao PtOs F Ca:P djusted I F
ratio Ca:PI PI

9er cent percent per centt w cent moles moles ILM LM x 3 P-V
I (1.593)* 0.09 53.27 42.07 0.17 1.603 1.594 11 165 223
0.18 53.22 42.02 0.18 1.604 1.595 10 162 236
0.91 53.57 41.15 1.29 1.648 1.589 20 1650 1690
K (1.628) 0.09 53.20 41.06 0.31 1.641 1.626 11 340 408
0.18 53.33 41.14 0.39 1.641 1.623 16 340 510
L (1.645) 0.18 53.58 41.33 0.19 1.641 1.632 11 147 250
Q (1.663) 0.095 53.90 41.03 0.16 1.663 1.656 8 99 210
0.95 52.89 38.24 1.81 1.751 1.662 13 2220 2380
I
See foot-notes in Table II.

ride concentration in the 1000 p.p.m. solution is about the same as that
in the 0.095 per cent solution in Table II, where mostly fluorapatite was
formed, the formation of CaFz in this case (Table IV) may possibly be ac-
counted for by the loo-fold difference in the ratio of solid to fluoride ion.
At this dilution considerably more apatite dissolves compared to the
amount of fluoride which reacted, so that the phosphate is not considered
in excess unless the concentration is greater than the calcium concentration.
Thus the liquid phase analyses indicate the occurrence of the same reactions
as those indicated by the solid Ca:P ratios. In the first half of Table V
are given liquid phase values of some of the apatites in which insufficient
material was available for complete solid analyses. Apparently at this
concentration fluorapatite has formed in all cases.
Dilute and Intermediate Values of Fluoride Concentrations at 100 (Tables
H. G. MCCANN 253

TABLE IV
Dilute and Intermediate Values of Fluoride Concentrations
2.5 gm. of hydroxyapatite treated at 37 with 10 liters of the indicated sodium
fluoride concentration.

Original Solid Liquid jolid*


rolution
Apatiti;ample - _ -
F cao PaOs F Ca:P i!Adjusted P Ca Sxcess P t F
Ca:Pt
.- -
y *er ml. fier cent per cent I,er CL% moles moles PM PM wf IIM
Q (1.663) 2 53.84 41.18 0.05 1.655 1.653 29 30 0 7
II (1.665) 2 52.97 40.50 0.20 1.656 1.646 27 55 0 26
5 53.08 40.60 0.22 1.655 1.646 16 28 0 29

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10 53.13 40.61 0.32 1.656 1.642 16 22 0 42
20 53.26 40.52 0.32 1.663 1.650 26 36 0 42
50 53.11 40.58 0.37 1.657 1.639, 22 30 0 49
100 53.15 40.49 0.31 1.662 1.648 35 39 0 41
200 53.27 40.24 0.66 1.676 1.645 48 8 40 87
500 53.40 39.71 1.32 1.702 1.640 123 3 120 174
1000 53.70 38.56
-I 2.43 1.763 1.645 145
-
2
I
140
I
320

* Concentrations are expressed in micromoles per liter in the liquid and micro-
moles per 0.25 gm. of the solid, so that direct comparison may be made.
t As in Table II.
f At this dilution, 100 times that of previous samples, the solubility of the apatite
in relation to thg amount of fluoride which reacted is considerably higher and phos-
phate is considered to be in excess only if its concentration exceeds that of the
calcium.

TABLE V
Dilute Values of Fluoride Concentrations
0.10 gm. of hydroxyapatite treated with 400 ml. of solution containing 5 p.p.m.
of fluoride at the indicated temperature.

Solid Liquid* Solid*


Apatite sample No. Temperature I-

F P Ca Excess P$ F
-~
C. per cent PM !JM PM PM
I 37 0.06 32 42 0 8
K 0.20 29 29 0 26
L 0.01 29 37 0 1
II 0.28 29 24 0 37
I 100 0.20 103 55 40 26
K 0.2 30 8 22 26
0.1 10 22 0 13
k 0.17 10 18 0 43

* See foot-notes in Table IV.


254 HYDROXYAPATITE-FLUORIDE ION REACTION

V and VI)-Up to 20 p.p.m. of fluoride, apatite Sample II forms only


fluorapatite, but, starting at about 100 p.p.m., ever increasing amounts of
CaFz are formed. At low fluoride levels apatite Samples L and Q also
form fluorapatite, but apatite Samples I and K release excess phosphate.
Since CaFz cannot form at this fluoride concentration, it is possible that
adsorbed phosphate is being released at this temperature. However, the
probability is that these samples are not stable at this temperature and
dilution and are becoming more basic in the boiling water, thus releasing
phosphate while at the same time forming some fluorapatite.

TABLE VI
Dilute and Intermediate Values of Fluoride Concentrations

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2.5 gm. of hydroxyapatite treated at 100 with 10 liters of the indicated sodium
fluoride concentration.
T T
Original Solid Liquid* Solid
solution
Apatit;;mple - T

F cao PlOl F Ca:P idjustec i P F


ratio ca:pt
____ -- .I- ~-__
y &?r ml. fit?7 cm t per cent per CL%t moles ?noles PM PM PM PM
I (1.593) 10 52.30 41.51 0.12 1.609 1.599 Lost 27 0 16
II (1.665) 10 52.20 40.00 0.33 1.653 1.637 1629 0 43
20 53.21 40.48 0.38 1.663 1.647 20 25 0 50
100 51.19 38.93 0.58 1.672 1.643 84 . 7 77 76
200 53.02 40.10 0.47 1.674 1.652 129 4 125 62
500 52.41 39.69 0.67 1.672 1.640 145 2 140 88
1000 53.11 38.40 2.18 1.751 1.641 1340 6 1330 287
- d- ,
* See foot-notes in Table IV.

Radioactive Hydroxyapatite-This material with a calcium to phosphorus


ratio of 1.641 is similar in this respect to apatite Sample L with a ratio of
1.645. The reactions with this material took place at a somewhat lower
temperature (20) and for a considerably shorter time than with other
samples, so that the attainment of equilibrium is less likely. As shown in
Fig. 1, there is a drop in both the calcium and phosphorus concentrations
at first, showing the decreased solubility of fluorapatite as compared with
hydroxyapatite. There is no indication of reabtion to form CaFz below
100 p.p.m., but at 1000 p.p.m. this type of reaction was extensive as indi-
cated by the higher P32 concentration in the filtrate. Apatite Sample L
showed a similar reaction at this low concentration at 37. It is interest-
ing to nobe that there is no sudden change in the type of reaction as the
solubility product concentration (about 25 p.p.m. of F, based on the solu
bility of the apatite in water) is passed, but that a change occurs gradually
as a level considerably above this value is approached.
H. G. MCCANN 255

Electrolytic Conductivity-It is interesting to note again that there is no


indication of any change in the type of reaction as the solubility product
concentration is passed. A change in the type of reaction at this point
would probably change the slope of the curve somewhat, due to a difference
in the ions released. However, a perfectly straight line was obtained up
to 50 p.p.m., as shown in Fig. 2.
E$ect of Bufering Solutions (Table VII)-The lower the pH, the greater
the solubility of the hydroxyapatite and hence the greater the amount of
CaFz formed from the dissolved calcium. After the acidity has been neu-

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3OOL y P in filtrate,

40 60 80 IOC 65 Oo IO 20 30 40 50
FLUORIDE ION IN FLUORIDE ION IN
ORIGINAL SOLUTION-y/ml. ORIGINAL SOLUTION-y/ml.
FIG. 1 FIG. 2
FIG. 1. The effect of F ion on radioactive hydroxyapatite, showing the concentra-
tion of Ca and P in the filtrates from 0.1 gm. samples of apatite treated at 20 with
500 ml. of the indicated F solutions.
FIG. 2. Electrolytic conductivity of solutions of apatite Sample II and F ion.

tralized by dissolving t.he hydroxyapatite, apparently considerable fluor-


apatite also forms.

DISCUSSION

These experiments show that the most important variables in the reac-
tion between fluoride ion and hydroxyapatite are the fluoride concentration
and the Ca: P mole ratio of the hydroxyapatite, with the temperature
playing a less important rBle. At 37 at a concentration of 5 p.p.m. of
fluoride, some fluorapatite is formed with all the samples of hydroxyapatite
tried. With 100 per cent hydroxyapatite, fluorapatite is formed almost
exclusively up to 0.1 to 0.2 per cent fluoride when small volumes of solution
are used (2.5 gm. per 100 ml. of solution), and up to 200 p.p.m. with large
volumes of solution (2.5 gm. per 10,000 ml. of solution) by exchange of
fluoride with hvdroxvl. At concentrations of around 0.1 or 0.2 wer cent
256 HYDROXYAPATITE-FLUORIDE ION REACTION

fluoride at 37, little or no fluorapatite is formed until the ratio of calcium


to phosphorus is over three-fourths of the way between t;icalcium phos-
phate (1.500) and hydroxyapatite (1.667). At 100 the formation of fluor-
apatite starts just a little over half way between the two, as indicated in
Fig. 3.
The formation of fluorapatite from hydroxyapatite (as contained in fer-
tilizer or bone) at fluoride levels in which the solubility product has not
been exceeded has been shown by several workers. MacIntire et al. (18)
TABLE VII
Effect of Buffering Solutions
2.5 gm. of hydroxyapatite Sample II in buffer at indicated pH; 0.09 per cent F
at. 37.

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Glycine buffer Solid

Ca:P
-
A
Filtrate
- I-
Solid

Original pH
I?inal pH Pa06 ratio P CC% PO F

ger Ge%L per cent her con nzoles moles PJf w /WX: I PM
2.95 7.40 52.99 39.56 1.36 1.696 1.631 342 12 1026 1790
3.93 7.38 52.85 39.90 0.71 1.677 1.644 197 6 591 930
5.97 6.90 53.19 40.33 0.39 1.670 1.651 84 12 252 510
7.97 6.99 53.20 40.39 0.36 1.667 1.651 81 12 243 470
8.95 8.54 53.04 40.47 0.25 1.659 1.648 65 12 195 330

5.07 6.33 53.44 40.58 1.16 1.667 1.614 1530


6.10 6.57 53.20 40.88 0.79 1.647 1.611 1040
6.98 7.23 53.18 40.99 0.61 1.643 1.615 800
8.00 8.33 53.04 40.80 0.27 1.646 1.633 360

See foot-notes in Table II.

found this to be the cause of the insolubility developed by certain phos-


phatic fertilizer mixtures on storage. Neuman et al. (19) demonstrated
that fluoride replaces either hydroxyl or bicarbonate ions in the surfaces of
mineral phase of bone. Megirian (20) confirmed these results with glycol-
ashed bone.
All these workers used very low fluoride concentrations and the evidence
for fluorapatite formation at higher concentrations has been very sparse.
Reference has often been made to the importance of keeping the fluoride
concentration at a level in which the solubility product is not exceeded
(19, 20). Syrrist (al), in a histological study of teeth exposed to a strong
NaF solution for 20 minutes in vivo, suggested the presence of fluorapatite
rather than calcium fluoride after extraction 1 week later. Variability of
H. G. MCCANN 257

reaction with fluoride with varying Ca: P ratio has been indicated. by
MacIntire et al. (22), who noted that a number of commercially prepared
calcium phosphates reacted in varying degree with CaFz to form fluorapa-
tite, pure hydroxyapatite being the most reactive.
The reaction of fluoride concentrations above 0.2 per cent has been
shown in the above experiments to form calcium fluoride in large amounts
with small amounts of fluorapatite also forming in certain cases with 100
per cent hydroxyapatite. This formation of calcium fluoride has been

IOO-

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80-

60-
\

iZ 1.500 1.580 1.600 1.620 1.640 l.66d


Co: P RATIO IN ORIGINAL APATITE
FIG. 3. Effect of Ca:P ratio of apatite on the type of reaction with 0.1 to 0.2 per
cent F. The ratio at Point 1 is that of tricalcium phosphate, at Point 3 that of hy-
droxyapatite, and Point 2 is midway between, a point at which the empirical compo-
sition 1s Ca9.s(P04)6(OH)1. The points on the 100 line represent reactions with
apatite Samples I, K, and Q, and on the 37 line with apatite Samples L and Q or II,
as estimated from the data in Tables II and III. Ca:P ratios have been adjusted
for Cl and CO2 content.

shown by several workers to be due to the double decomposition of calcium


phosphate by sodium fluoride to form calcium fluoride (23-26).
This reaction appears to take place on the surface of the crystals. Un-
less the fluoride concentration is very high, forcing a considerable break-
down of the hydroxyapatite structure, the amount of reaction as indicated
by the fluoride content of the solid changes but slightly with fluoride con-
centration in the solution. Thus the per cent of fluoride in apatite Sample
II ranges from 0.2 per cent to 0.3 per cent as the fluoride concentration
increases from 2 to 100 p.p.m. There is more of a change in the amount of
fluoride picked up by apatites with similar Ca:P ratios but different surface
areas than there is among apatites with widely different Ca: P ratios and
similar surface areas. However, the type of reaction which takes place is
dependent to a great degree on the hydroxy concentration on the surfaces.
258 HYDROXYAPATITE-FLUORIDE ION REACTION

SUMMARY

The reactions between fluoride ion and hydroxyapatite were investigated


over a fluoride range of 1 p.p.m. to 9.5 per cent, and over a calcium to
phosphorus ratio in the apatites of 1.593 to 1.665, with results indicating
that the type of reaction is chiefly dependent on these two variables.
Fluorapatite is formed at all ratios of Ca: P at a few parts per million of
fluoride, calcium fluoride or fluorapatite is formed up to 0.2 per cent fluo-
ride, depending on the Ca:P ratio, and calcium fluoride is formed at all
ratios at high fluoride concentrations.

We are indebted to Dr. F. J. McClure, Chief of the Division of Oral and


Biological Chemistry, National Institute of Dental Research, who sug-

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gested the problem and contributed many helpful ideas, to Dr. R. C. Likins,
who suggested and assisted in the preparation of the radioactive hydroxy-
apatite and did all the counting of the samples, and to Mr. F. A. Bullock,
who performed a portion of the analytical work.
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REACTIONS OF FLUORIDE ION WITH
HYDROXYAPATITE
Harold G. McCann
J. Biol. Chem. 1953, 201:247-259.

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