A modelfor recording mercury release from an amalgamsurface

Dag Brune
NIOM Scandinavian Institute of Dental Materials, Forskningsveien (Received 20 November 1984; revised 14 February 1985) 1, 037 1 Oslo 3, Norway

The release rate of mercury from a conventional, under static conditions in stimulated exponentially artificial

a dispersed phase or a spherical high copper content amalgam saliva than in

or artificial saliva has been measured and found to decrease approximately

with time. A higher initial release rate was observed for mercury in stimulated

saliva during the in vitro experiments. exponentially with time. After brushing the surface of the amalgam during two an increase in corrosion current was measured surface has been proposed.

In a pilot study corrosion current was recorded from an amalgam specimen immersed in saliva, and was found to decrease approximately subsequent periods, in a manner similar to toothbrushing,

indicating the removal of loosely bound corrosion products. A model describing the periodical mercury release from an amalgam
Keywords: Dental materials. mercury release, amalgam corrosion, saliva

During exposure of an amalgam restoration to chewing forces mercury might be released. The levels of mercury in the mouth air and blood before and after chewing have been measured in a group of individuals with amalgam restorations as well as in a control group without such restorations. Significantly higher air mercury levels were demonstrated after chewing than before chewing. The blood mercury concentrations were found to be positively correlated with the surface area of the amalgam restorations. An in vitro approach to simulate the mechanical interactions involved in chewing is accomplished by so-called cyclic loading. During such interactions considerably higher release rates of mercury were registered in artificial saliva3 than under static conditions4f5. A substantial part of the mercury released from the amalgam surface is present in amalgam particles3* 5. It is known that various types of corrosion products of tin are deposited on amalgam surfaces, and may possibly act as a semi-protective layer, reducing the corrosion rate. According to ESCA-measurements (electron spectroscopy for chemical analysis) such corrosion products have been found to be loosely bound to the surface and may be removed from the surface by a brushing procedure similar to toothbrushing in vitro8. After brushing a clean surface is obtained. Exposing such a surface to an electrolyte, electrochemical corrosion could be expected to be pronounced, resulting in the release of Hg2+(Hg2) ions. In addition, unreacted mercury, i.e. Hg, could be released from the surface. Presently, the static release pattern of mercury in at-tifical and natural saliva was studied in vitro in order to obtain knowledge about the release rate versus time, as well as about possible migration of mercury corrosion products
0 1985

through the pellicle which is deposited on a restorative material like amalgamg. Furthermore, the effect of brushing an amalgam surface on corrosion current was studied. MATERIALS AND METHODS

Amalgams. The release of mercury in both natural and artificial saliva was studied on 4 freshly prepared cylindrical specimens of the product Dispersallo\$, 8 mm high and 3 mm in diam. (Table 1). The alloy powder was triturated with radioactive mercury (Hg, 203Hg). The radioactive specimens were exposed to natural or artificial saliva, about 10 min after mixing, for a period up to about 13 h. The samples were not polished. During these initial release measurements cylindrical specimens were considered in view of rapid preparation of such samples allowing measurements to be conducted soon after trituration. For the same reason the samples were not polished. Also the release of mercury from old amalgam specimens, i.e. about 1 mnth old, was studied on 4 specimens each of a conventional, a dispersed phase and
Table 1 Amalgams studied Type Conventional Name Revalloy@ Manufacturer S.S. White Ltd. Middlesex. England Batch no. 117234

Dispersed phase

Dispersalloy@

Johnson b Johnson, 8L 713 Dental Products Co., E. Windsor, NJ, USA Kerr Mfg Co., Rochester, NY, USA 1027752289

Spherical high copper content

SybraloP

Butterworth Et Co (Publishers) Ltd. 0142-9612/85/050357-03$03.00 Biomaterials 1985, Vol 6 September 357

A model for periodical mercury release: 0, &me

a spherical high copper content amalgam type immersed in artificial saliva (see Table 7). These specimens consisted of rectangular sheets, measuring 5 X 10 mm with a thickness of about 0.3 mm. The samples had been ground with 1000 grit paper. The nuclear technique used has been described previously5* lo. Saliva. The saliva comprised either natural saliva collected under stimulated conditions by chewing parafilm, replaced at intervals between 10 and 30 min, or artificial saliva of the modified Fusayama type containing no proteins. The amalgam specimens were immersed in 7.5 ml of the saliva solutions, at 37C. while stirred under aerated conditions. During the 10 to 30 min time periods proteins in the natural saliva samples were not observed to precipitate, and the pH remained between 6.5 and 7. Corrosion current measurement. The total corrosion current from 1 specimen of dispersed phase amalgam was measured against a Pt-electrode by means of a galvanometer with an inner resistance of 10 kn while the amalgam specimen was immersed in stimulated saliva at 23C. Currents were registered during a period up to about 36 h. The amalgam specimen was brushed in 2 periods on one side with a toothbrush to simulate toothbrushing, once for 10 s and again for 20s. Toothpaste was not used during these measurements. Corrosion current following this procedure was measured.

0.5

rT

0.1 N E 0 ;: 0.05 0.01

0 Dispersalloy 0 Revalloy Ei Sybralay

, 0.005 * 0.001 o.oooe

50 Time(h)

Id0

Figure 2 Release rare understatic conditions for totalmercury from 3 types of amalgams of age about 1 mnth

deposited quickly in a l-2 nm thick surface layer (ESCA-information depth) of an amalgam immersed in vitro in natural saliva. These elements are the main constituents of the saliva proteins*, while the rapid deposition of these elements indicate the fast deposition of the pellicle. Mercury seems to have migrated through such layers under the present static release conditions (Figure I). This seems also to occur under dynamic conditions, i.e. during cyclic loading13. Current measurement. Figure 3 illustrates the total corrosion current versus time for the amalgam sample exposed to the saliva. An approximate exponential decline was observed in this pilot study. A substantial fraction of the current could probably, in this case, be ascribed to corrosion of zinc and tin5-7. After cleaning the amalgam surface by brushing a strong increase in the current was observed. In this case corrosion products of tin deposited on the amalgam surface seems to have been removed by brushing as indicated by ESCA-measurements. Release under dynamic conditions. A high release rate of total mercury, i.e. mercury in all chemical forms occurs during cyclic loading in stimulated saliva13 analogous to the conditions in artificial saliva3. Amalgam particles are mainly released. Elemental mercury (Hg) is also released during the action of forces. Ionic mercury may be released through

RESULTS AND DISCUSSION

Static release measurements. Figure I represents the static release rates of total mercury (all forms) in natural or artificial saliva. The release rates in both cases decline approximately exponentially with time. A higher release rate was indicated in the stimulated saliva than in the artificial saliva in the initial release phase. Figure 2 presents static release rates for 3 types of amalgams immersed in artificial saliva. The samples were about 1 mnth old. Figure 1 pertains to an initial release period shortly after trituration, i.e. from freshly prepared samples, while Figure 2 concerns the release from old samples. The decline in the release rate was especially pronounced for the freshly prepared specimens (Figures 1 and 2). According to ESCA-measurements, it has been shown that the elements carbon, oxygen and nitrogen are

Total electrochemical

release

Me*Me2*+

2e-

0 Natural saliva a Artificial saliva

50
aI

'0 : 30 N E 4 a IO

c
0
2 Time (h) 3 10s brushing

it
2 bruz Time (h)
)S

36 +

Figure 1 Static relese rate of total mercury versus time in stimulated and artificial saliva. The release rate refers to 4 freshly prepared specimens of a dispersed phase type amalgam. Each bar with standard deviations represents the mean value of 4 measurements.

Figure 3 Corrosion current from 1 amalgam specimen measured against a Pt-electrode versus time. The amalgam surface has been brushed in 2 periods.

358

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1985, Vol6 September

A model for periodical mercwy release: 0. Brune

Dynamic

Dynamic :
I

Dynamic :
I

II II II ii ; II1 ,,,
III III I II I iI I II I II I : iii

II II II II I
Static ii i
I I I I I I I I II II II II II II II i

II II II
II I

Static

iii
I II I II I I; I II I II I II I II :

Static

Adaption of the model to clinical conditions. In order to predict mercury release in the oral cavity under different clinical conditions various parameters inherent with masticatory functions (chewing habits) e.g. chewing time, frequency of meals, application of various mastical forces and brushing the amalgam restorations etc., should be considered in detail. Clinically, static release conditions may exist during rest periods e.g. between meals. Deposits on the amalgam surface may be removed by mechanical interactions inherent with the chewing processes, whereby corrosion products may be removed through scratches in the pellicle film.

ACKNOWLEDGEMENTS
The author wishes to express his gratitude to Dr G. Hultquist, Royal Institute of Technology, Stockholm, Sweden for kindly conducting the corrosion current measurements and to D.M. Evje, NIOM, for skilful technical assistance in the various experimental procedures.

Ii
Time (h)

18

24

Figure 4 Scheme of model for mercury release (all chemical forms) from an amalgam surface under dynamic and static conditions.

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The periodical release model. Based on another study13 and present findings a model describing the mercury release pattern during dynamic and static conditions is proposed, and schematically outlined in Figure 4. The model involves high mercury release rates (mercury in all forms included) during loading13, followed by decreasing release rates under the subsequent static conditions.

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