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COMPOSITION OF DENTAL ENAMEL /. A.

Weatherell

consists chiefly of calcium, phosphate and hydroxyl ions in a


stoicheiometric ratio Ca10(PC>4)6(OH)2, each crystallographic
unit cell consisting of 18 ions arranged as hydroxyapatite.
A reactive part of the hydroxyapatite structure is the column
of hydroxyl ions parallel to the long axis of the crystal.
COMPOSITION OF DENTAL ENAMEL Invariably, some of these hydroxyl ions are missing, and this
allows increased ionic movement within the column, thereby
increasing its chemical reactivity. Other hydroxyl ions can be
replaced by fluoride; this probably restricts the mobility of the
J. A. WEATHERELL B.Sc. Ph.D. hydroxyl ions in the column, resulting in stronger bonds with
Department of Oral Biology adjacent calcium ions, making the crystal as a whole more
Dental School, University ofLeeds stable and facilitating crystal formation (Posner & Eanes,
1963). Calcium and phosphate ions can also be substituted.
1 General chemistry of enamel
2 Minor constituents in enamel 2. Minor Constituents in Enamel
3 Chemical variations within the enamel
4 Chemistry and caries The fact that the enamel mineral is hydroxyapatite with this
References capacity for ionic exchange ensures that the enamel contains at
least trace amounts of other elements, e.g. Na, Mg, Zn, K,
Interest in the chemistry of dental enamel is closely linked with Pb, Sr, Fe, F and other minor ionic components, e.g. carbonate.
concern about the problems of dental caries. Recent work has These can be incorporated while the apatite crystallites are
recognized the importance of enamel as an integrated biological forming or by hetero-ionic exchange reactions at crystallite
structure. Its heterogeneous nature cannot be understood surfaces.
without appreciating what influence the process of enamel Most of the minor ionic components in enamel are no doubt
formation has upon its subsequent chemistry and properties. properly considered as part of the apatite crystal structure,
Also, if the pattern of carious attack is to be explained, infor- but others probablyresideat least in part on the surfaces of the
mation must be available about any systematic chemical apatite crystallites or as a separate phase. For instance, al-
variations within the enamel and their possible influence on though carbonate can be accommodated to a certain extent
the rate of carious destruction. In this discussion, an attempt within the lattice, replacing phosphate and to a lesser extent
has been made in the light of recent investigations (Weatherell, hydroxyl ions, some of it may be situated at the crystallite
Robinson & Hallsworth, 1974) to put the chemistry of enamel surface and could even exist separately as calcium carbonate
in such a context. (Elliott, 1969). At least part of the magnesium and other ions
such as citrate, too large to fit easily into the lattice structure,
are probably outside the body of the crystallites.
1. General Chemistry of Enamel
The most mineralized of all biological tissues, with a density
much greater than the dentine upon which it sits (fig. 1), FIG. I. Density of enamel and dentine, determined
enamel consists largely of inorganic material in the form of by a floatation technique
small crystals. These are visible only in the electron microscope
and, for this reason, are usually called crystallites. The in- 3.0-1
1
organic material consists mainly of calcium phosphate and,
judging from x-ray and neutron diffraction data and from
infrared studies, it is essentially similar to the group of minerals
known to geologists as apatites (Kay, Young & Posner, 1964).
It is likely that calcium-deficient apatitic structures are present.
S
These might explain the sometimes low calcium: phosphorus
ratios, e.g. in the tooth surface (Wirsing, Judd & Ansell, 1974). ENAMEL| DENTINE (PULP
o
The possibility that minor amounts of other, non-apatitic
2.5-
crystal forms exist in enamel has also been suggested: octa- a.
calcium phosphate (Brown, 1966), perhaps as a residue of "5
mineral present during the developmental stages of mineraliza-
tion, and dicalcium phosphate (Casciani, 1971) and (i-tri-
calcium phosphate (Vahl & Pladkova, 1967), perhaps as a
result of post-eruptive alterations brought about in the tooth
surface. It is thought, however, that any such non-apatitic
components of the mineral, if present, constitute a very small
part (under 2 % by weight) of the total inorganic material and, 2.0
from the point of view of its general chemical composition,
enamel can be considered to consist mainly of hydroxyapatite
(Young & Spooner, 1970). Distance from
enamel surface to pulp (mm)
The structure of the geological and synthetic apatites is
well established, and it has been presumed by analogy, together Eight specimens of enamel and 12 specimens of dentine were dissected
with the results of chemical analysis, that the enamel mineral from » I OOnm-thlck section of a tooth

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Vol. 31 No. 2
COMPOSITION OF DENTAL ENAMEL /. A. Weatherell

The concentration of any particular ion in enamel seems to mature tissue have arrived at widely differing values, from
depend directly upon its concentration in the environment 0.36% (Eastoe, 1960) down to 0.06% (Glimcher, Friberg &
during development when the crystallites are forming and, Levine, 1964; Weidmann & Eyre, 1967). In hindsight, the
although generally to a lesser extent, upon its concentration in most likely reason for the discrepancies is that most of the
the food and water ingested after tooth eruption. Its concentra- analyses were carried out on samples pooled from large num-
tion also depends upon the rate at which the ion is absorbed bers of teeth. Sampling techniques varied and different regions
at the tooth surface, being influenced by the physical condition of enamel were studied.
of the enamel, its degree of mineralization and the pH at the
enamel-environment interface.
3. Chemical Variations within the Enamel
The best documented account of the factors influencing the
concentration of an extraneous ion in enamel concerns Enamel is a heterogeneous structure, its composition varying
fluoride and, since the factors governing fluoride uptake are markedly from surface to interior and also from one region of
probably pertinent to the uptake and distribution of several the tooth to another. In considering its nature and properties,
other ions, they can profitably be mentioned in some detail this cannot be ignored; it is essential to sample carefully defined
here. areas if chemical analyses of either the inorganic or the organic
There is a well-established relation between the concentra- components are to be meaningfully compared.
tion of fluoride in the diet and drinking-water and its con- Analysis according to density, for instance, shows that the
centration in enamel (Brudevold, 1962). Any increase in the total amount of material per unit volume always decreases from
availability of fluoride from extraneous sources, e.g. as a surface to interior. The patterns of calcium and phosphate
result of the fluoridation of water supplies, the presence of a distribution per unit volume of enamel are, as would be
silicate restoration, or the application of fluoride-containing expected, fairly similar to those of density, concentrations
solutions to the tooth surface, is reflected by an increased decreasing from surface to interior. In general, over-all density
concentration of fluoride in enamel. and mineral concentrations tend to be lower in the enamel
Fluoride is taken up most rapidly by enamel that is only near the cervical region of the tooth, immediately beneath
partially mineralized. Uptake is thereforerelativelyhigh during the cusps, and below the fissures of molars and the pits of
the formative period, which is why, to be an effective public incisors (Weatherell & Robinson, 1973). Mature enamel
health measure, fluoridated water supplies should be available consists almost entirely of apatite crystallites and presumably
prior to tooth eruption. If, however, the enamel is incompletely the explanation for changes in density, calcium and phos-
mineralized or becomes partially demineralized, even after phorus concentrations is that the amount of extra-crystallite
eruption, fluoride is again rapidly incorporated. This explains space varies, increasing towards the enamel-dentine junction
the invariably high concentration of fluoride in carious lesions and in the other less highly mineralized regions.
or in other porous imperfections of enamel and would appear The concentrations of minor inorganic ions also vary accord-
to be the principal reason why a low pH at the tooth surface ing to consistent patterns, although not all constituents are
enhances fluoride uptake; presumably the acid demineralizes distributed in the same way. Concentrations of carbonate,
the enamel to some extent. sodium and magnesium are relatively high in the interior and
There are instances in which elements other than fluorine diminish towards the surface. The reason for this is not clear
have accumulated in enamel. Abnormal concentrations of lead and there are several possible explanations.
have been associated with cases of lead poisoning (Brudevold If some of these ions are chiefly located at crystallite surfaces,
& Steadman, 1956). Strontium is readily absorbed and the the lower concentration near the tooth surface might merely
well-known ability of teeth to accumulate 90Sr has been used as reflect a decrease in the surface: mass ratios of the crystallites
a means of monitoring the extent of atomic fall-out (Starkey & in this region. The distribution pattern of sodium, on the other
Fletcher, 1969). hand (Besic, Knowles, Keller & Wiemann, 1970), could
Discussion of the mineral would not be complete without indicate the distribution of water in the enamel.
some mention of the water present in enamel, which can Some of the distribution patterns might reflect events that
contribute up to 3 % of its weight. There is unfortunately no occurred during the period of enamel formation and early
clear consensus of opinion about the nature of this water, mineralization. If, for instance, the carbonate of enamel were
despite numerous investigations, mainly with the use of nuclear- to originate as carbon dioxide produced by the ameloblasts
magnetic-resonance techniques (e.g. Myers & Myrberg, 1965). as they advanced to the outer limit of the tissue during the
In one such investigation three types of water were reported, period of enamel formation, the amount of carbonate deposited
some of which was free and some "freely tumbling water but in the mineral would depend on the metabolic activity of the
'caged' within the structure" (Little & Casciani, 1966). Other enamel-producing cells. The more active they were, the more
workers have disagreed, however, with this description. carbonate would be incorporated into the forming mineral.
The older but still attractive concept of Neuman & Neuman As their activity decreased towards the outer enamel, less
(1958) suggests that a small but chemically significant part of carbon dioxide would be produced and the amount trapped by
the water might be present in the form of hydration shells the forming enamel crystallites would therefore fall. A similar
enveloping the crystallites. Representatives of many of the explanation could account for the distribution pattern of
ions mentioned above, particularly those associated with magnesium, if its origin, too, were related in some way to
outer regions of the crystallites, would be associated with the cell function.
water molecules in these hydration shells. Ionic exchange The distribution of most other trace elements is usually the
reactions would occur most rapidly in this region. reverse of that associated with carbonate, sodium and magne-
It is also highly probable that some of the water in enamel sium, concentrations being highest near the tooth's surface
will be bound to the small amounts of proteinaceous material and decreasing towards the interior. These ions are mainly
present. Estimations of the actual amount of protein in the exogenous in origin and accumulate principally by ionic

116

Br. Med. Bull. 1975


COMPOSITION OF DENTAL ENAMEL /. A. Weatherell

FIG. 2. Fluoride distribution in the enamel of FlG. 3. Contours of density (expressed in g/cm1) in
lOOum-thick section from a human molar an enamel section from the cusp of a permanent
molar

The fluoride content of small enamel particles dissected from the


section was determined by use of the Orion fluoride electrode

exchange at the tooth's surface. As mentioned in section 2, from protein of oral epithelium or stratum corneum than to the
the manner of fluoride uptake it appears that most of this proline-rich organic matrix of forming enamel. It seems pos-
exchange takes place before eruption, when enamel is relatively sible that the tuft material in mature enamel originates during
permeable. The rate of incorporation slows down as enamel development, but perhaps constitutes part of the protein laid
becomes more mineralized. Once enamel is fully mature, down before the ectodermal cells of the inner enamel epithelium
probably within, say, two years after eruption, the rate of have fully differentiated into amelogenin-secreting ameloblasts
uptake is considerably reduced. The chemistry of the bulk of (Robinson, Lowe & Weatherell, 1975).
the enamel is therefore mainly established before eruption and There is relatively little organic material in the main body
seems to remain essentially unaltered throughout the tooth's of the enamel but the concentration often rises again at the
life. Only in unusual circumstances, if for instance concentrated enamel surface. This is, however, attributable to the presence
solutions of ions are applied to the tooth, is the composition of an organic pellicle consisting of oral debris and, in those sites
of the sound mature enamel drastically altered. protected from wear, perhaps including residual cellular mater-
In the enamel interior, the concentration of most of these ial from the layer of ectodermal cells which originally formed
trace elements is relatively low although, again, apart from the inner enamel epithelium. This organic layer, whether on
fluoride studies there is little detailed information about any
internal variations. In the case of fluoride, where enamel den- FlG. 4. Fluoride concentration (expressed in p.p.m.)
sity is low, e.g. near the amelo-dentinal junction, concentra- in different areas of a premolar from a 44-year-
tions of the element tend to be raised (fig. 2). The probable old subject
reason is that, where enamel density is low, there is more inter-
crystallite spacefilledwith organic material and water, and the Severe wear
200
enamel in such a region is more permeable. The same con- 2000T

siderations will probably apply to internal variations in the


concentration of other trace elements.
On a dry-weight basis, calcium and phosphorus gradients 1500
are more variable than on a volume basis and this itself is
perhaps an indication of the variations in the amount of organic
material situated in the space between the crystallites. The 1000-
amount of organic material present in mature enamel is some- BUCCAL
what small for accurate detailed analysis to be carried out
although qualitative information about its distribution has 500
been obtained from histological studies, and there have been
some attempts to determine its distribution quantitatively
(Wachtel, 1959; Robinson, Weatherell & Hallsworth, 1971).
Relatively large amounts of protein are present near the dentine,
apparently associated with the structures known to histologists
as enamel tufts; this is no doubt why enamel density sometimes
falls steeply near dentinal cornua (fig. 3). In vivo, there is prob-
ably also water bound to protein in this area, although the
details of the mineral-water-organic material relations in
enamel are not known and, at such low concentrations, the
direct determination of water introduces considerable technical
problems.
The relatively large amounts of protein present near the
enamel-dentine junction are probably a residue of the organic Loss of penkymata
matrix of forming enamel, most of which is withdrawn during Each curve represents the gradient In fluoride concentration from
the process of mineralization. Amino acid analysis, however, surface to interior of enamel, each point on the curves representing
reveals a composition somewhat closer to the ectodermal the fluoride concentration in a layer of enamel about 20jim thick

117

Vol. 31 No. 2
COMPOSITION OF DENTAL ENAMEL /. A. Weatherell

the tooth surface or in fact a part of it, might protect the It has been mentioned in section 3 that much of the fluoride
enamel from carious attack and is in this sense functionally originally present in the outer region of enamel of a newly
part of the tooth, although it should not strictly be regarded as erupted tooth is subsequently removed by wear. This is no
part of the true enamel structure. great disadvantage so far as caries is concerned, however, for
The original surface region of the enamel is, however, such loss of fluoride does not occur in those sites most suscep-
clearly different from the interior in a number of other ways. tible to carious attack; the most susceptible sites are the so-
The tendency for extraneous elements to accumulate by ionic called "stagnant" regions of the dentition where abrasion is
exchange makes the composition of the outer region, say minimal. In such sites, fluoride concentrations probably
30 (xm, significantly different from that of the deeper regions. increase with time, particularly when the fluoride content of
The gradients in density, calcium, phosphate, carbonate and the diet and the drinking-water isrelativelyhigh. Such stagnant
magnesium concentrations also give the surface special chemi- regions are also usually covered by plaque, an organic layer
cal characteristics. produced by and including oral bacteria trapped within it2.
The composition of the surface is not static; it changes The acid produced by these plaque bacteria lowers the pH at
constantly with age. In some areas, particularly where the the tooth surface. This can destroy the enamel but it also
enamel surface has been affected by the low pH of an overlying increases the rate of fluoride incorporation, partly because the
plaque, fluoride and probably other trace elements increase in • acid increases the enamel's porosity and therefore the surface
concentration. Elsewhere, slight abrasion gradually removes area available for exchange reactions, but probably also because
much of the original surface together with a large proportion the fall in pH itself increases the rate of fluoride exchange
of the tooth's high-fluoride enamel. In districts where the per se. This mechanism may be extremely important, for an
fluoride content of the drinking-water is low, the high fluoride acceleration of fluoride uptake at the site of attack might halt
concentration in the enamel surface can be irrevocably lost, or even reverse the process of enamel destruction. Indeed, it
although in high-fluoride districts it might to some extent be seems possible that the chief value of topical fluoride treatment
restored by post-eruptive uptake of fluoride from the saliva. is to introduce fluoride to the forming lesion, the amount
Where abrasion is severe, most of the enamel is worn away and absorbed being much larger and probably more significant so
the new surface has the low density, high carbonate, high far as caries inhibition is concerned than that taken up by
magnesium and low fluoride concentrations characteristic of sound enamel. Recent work by J. L. Hardwick might be
interior enamel (fig. 4). similarly explained. Hardwick (personal communication)
found in experiments with rats that caries inhibition was
greater when the fluoride was added to the diet than when it
4. Chemistry and Caries was administered in the drinking-water, despite the fact that,
Investigations into the chemical composition of dental in general, fluoride is absorbed more easily from drinking-
enamel have not been carried out merely as an academic exer- water. A possible explanation is that the fall in pH induced
cise. Attempts to control dental caries require information by the large quantity of sugar in the cariogenic diet would cause
about any relation between the quality of enamel and its the plaque pH to fall and accelerate the uptake of fluoride into
resistance to carious attack. underlying incipient lesions. It is also of some interest to note
It is because of the special clinical dental interest in the in this connexion that cervical regions of teeth are not especially
benefits of fluoridation1 that the uptake and distribution of prone to caries, despite the fact that these regions tend to be
fluoride in enamel has received so much attention. The most covered by plaque and the enamel usually shows signs of
widely accepted explanation for its anti-caries effect is that it demineralization or change. In fact, this region of enamel tends
makes the enamel mineral more resistant to acid produced by to have a high and apparently increasingfluorideconcentration,
bacteria at the tooth surface. As mentioned in section 1, no doubt partly because of the effect of the low plaque pH;
fluoride can exchange with hydroxyl ions in the crystal lattice. and this high fluoride concentration may be one reason why
This stabilizes the structure and facilitates apatite formation, cervical enamel is relatively resistant to caries.
probably by increasing the degree of hydrogen bonding in the The carbonate ion, which tends to introduce disorder into
hydroxyl column. It has been shown experimentally that the apatite crystal lattice, has also received some attention.
fluoridated apatite is more crystalline, at any rate in bone Carbonate is smaller than phosphate and when it replaces
(Posner & Eanes, 1963), and it seems likely that fluoridated phosphate will tend to reduce lattice dimensions. It is, on the
crystallites tend to be larger, with a smaller surface area per other hand, bigger than hydroxyl and when itreplaceshydroxyl,
mass of mineral. All this reduces the ease with which enamel the lattice will expand (Elliott, 1969). The presence of carbonate
mineral dissolves in the acid produced by bacterial fermenta- in enamel, probably for this reason, introduces strain into the
tion. structure of the apatite lattice and increases the ease with
The highfluorideconcentration in the outer region of enamel which the enamel mineral dissolves in acid.
has, not surprisingly, been regarded as a principal defence Carbonate was regarded by both Hardwick (1949) and by
against carious attack. There is an established positive correla- Sobel (1962) as a possible Achilles' heel, enabling acid to
tion between the fluoride content of enamel and the incidence penetrate the enamel structure. There is no definitive proof
of dental caries, although the work of Brudevold (1962) that this is the case, although acid and carious attack both seem
suggests that a concentration of about lOOOp.p.m. in the outer to remove carbonate preferentially (Johansen, 1962). Recent
region of the enamel gives optimal protection against caries; analyses of samples of enamel dissected from thin sections of
and it is worth noting that higher concentrations can be asso- carious lesions (Hallsworth, Weatherell & Robinson, 1973)
ciated with abnormal, fluorotic, enamel. suggested that the earliest histological changes were associated

» See Jenkins, pp. 142-145 of thli Bulletin.—ED. * See Hmrito & Bowden, pp. 131-136 of thh Bulletin.—ED.

118

Br. Med. Bull. 1975


COMPOSITION OF DENTAL ENAMEL J. A. Weatherell

with the removal of mineral rich in both carbonate and mag- site. Johnson (1966) and J. Arends (personal communi-
nesium. Perhaps Hardwick's and Sobel's Achilles' heel should cation), for instance, have shown that the process of carious
have included magnesium as well as carbonate. It is unfortu- attack and the acid destruction of enamel crystallites in vitro
nately not known where carbonate and magnesium are located involve the preferential dissolution of crystallite cores. Arends
in the enamel structure, but the amount dissolved during the suggests this is explained by the presence of linear dislocations
initial attack seemed too great to be explained by a direct passing through the centres and parallel to the long axes of the
stoicheiometric dissolution of hydroxyapatite. If an initial enamel crystallites, although, as he points out, the possibility
inroad into the mineral fraction were to be made by the that the centres of the crystallites are chemically different
removal of a small amount of non-apatitic mineral, access to from the remainder cannot at present be ruled out. Here, as
and dissolution of the remaining apatitic material could be in the case of the histopathological pattern of carious attack,
greatly facilitated. it is often extremely difficult to distinguish between the influence
At a histological level, caries appears to penetrate enamel of chemical composition and the possible effect of structural
via the striae of Retzius, passes along the interprismatic variations on the progress of attack. As indicated in this paper,
pathways into the cross-striations of the prisms and, finally, however, chemical composition and tooth surface structure
into the prism cores (Darling, 1959). It has been suggested are inextricably linked and it is essential to consider the
from qualitative histological studies that these pathways chemistry of enamel within its developmental, histological
contain relatively high concentrations of organic material. It and anatomical context.
also seems possible that the carbonate- and magnesium-rich
mineral lost from the translucent zone is removed from these
pathways, judging from circumstantial histological evidence ACKNOWLEDGEMENTS
obtained by examination of areas sampled by Hallsworth I should like to acknowledge the fact that the original work
et al. (1973). Definite evidence is, however, lacking and it may described in this paper was carried out jointly with other members of
well be that the first mineral to be removed from the tooth during the Department of Oral Biology at the Dental School, University of
Leeds. I also wish to thank the Medical Research Council of Great
carious attack is not associated with any visible histological Britain for the generous support given to much of the work described.

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