Location via proxy:   [ UP ]  
[Report a bug]   [Manage cookies]                

Increased Mercury Emissions From Modern Dental Amalgams

Download as pdf or txt
Download as pdf or txt
You are on page 1of 7

Biometals

DOI 10.1007/s10534-017-0004-3

Increased mercury emissions from modern dental amalgams


Ulf G. Bengtsson . Lars D. Hylander

Received: 7 February 2017 / Accepted: 11 February 2017


© The Author(s) 2017. This article is published with open access at Springerlink.com

Abstract All types of dental amalgams contain exist no limit for maximum allowed emission of
mercury, which partly is emitted as mercury vapor. mercury from dental amalgams. These modern high
All types of dental amalgams corrode after being copper amalgams are nowadays totally dominating
placed in the oral cavity. Modern high copper the European, US and other markets, resulting in
amalgams exhibit two new traits of increased insta- significant emissions of mercury, not considered
bility. Firstly, when subjected to wear/polishing, when judging their suitability for dental restoration.
droplets rich in mercury are formed on the surface,
showing that mercury is not being strongly bonded to Keywords Mercury · Non-gamma-two ·
the base or alloy metals. Secondly, high copper Non-ɣ2 · Copper amalgam
amalgams emit substantially larger amounts of mer-
cury vapor than the low copper amalgams used before
the 1970s. High copper amalgams has been devel- Introduction
oped with focus on mechanical strength and corrosion
resistance, but has been sub-optimized in other The vast majority of mercury containing fillings
aspects, resulting in increased instability and higher consists of two principal ingredients; liquid mercury
emission of mercury vapor. This has not been and a metal powder referred to as the alloy. The
presented to policy makers and scientists. Both low mixing ratio is approx. 50 wt% of each with small
and high copper amalgams undergo a transformation variations, although alloys with high content of
process for several years after placement, resulting in spherical alloy particles requires somewhat less
a substantial reduction in mercury content, but there mercury (Anusavice et al. 2012). This mixing is
referred to as trituration by dental science.
The term alloy, when used in physics, refers to one
Ulf G. Bengtsson—Retired or more elements, at least one being a metal, which
are dissolved into each other. When used by dental
U. G. Bengtsson
science, alloy refers to a mixture of solid metal
Department of IEI, Linköping University, S-581 83
Linköping, Sweden particles, not including mercury apart from very
small amounts sometimes added (pre-amalgamation).
L. D. Hylander (&) When the bulk of mercury is added to the alloy
Department of Energy and Technology, Swedish
powder, reactions take place and the resulting
University of Agricultural Sciences, S-750 07 Uppsala,
Sweden compound is called dental amalgam. Amalgams are
e-mail: Lars.Hylander@slu.se mixtures of mercury and one or more other metals,

123
Biometals

which may be dissolved into the mercury or being considerably less mercury. This phase transformation
metal particles just glued together by mercury goes on for years constantly generating free mercury
(Hylander and Plath 2006). Silver, being the main (Schmalz and Arenholt-Bindslev 2009; Mahler et al.
component of the presently dominating alloy, has 1973).
resulted in the name silver fillings of these restora- Standards for the composition below refers to the
tions. Considering that mercury, not silver, is the alloy ingredients, not the final filling material.
dominating metal in the final filling, they should
rather be termed mercury fillings.
The alloy/mercury mixing ratio is set by the Methods used and types of amalgams
manufacturer at a ratio, where the mercury has been
claimed to be firmly bound to the alloy in the dental This study is based on observations of droplets rich in
amalgam. Although this assumption has been proved mercury found on dental fillings, challenging the
to be erroneous (Homme et al. 2014), there is no dominating assumption that mercury in amalgam is
consensus on acceptable emissions from dental firmly bonded to the alloy. The observations were
fillings and there is no awareness of differences in photographed with a light microscope (9252 magni-
mercury losses from conventional amalgams and fying), analyzed with a scanning electron microscope
non-ɣ2-amalgams, respectively. In addition, a limited (SEM) and a literature review was performed to
number of dentists prefer a softer mix, using an explain the phenomena and possible implications of
increased amount of mercury. This is known in dental these observations at the surface of dental amalgam
science as the “wet technique” (Möller 1978; fillings. The study includes two groups of dental
Bergdahl 1973). The excess mercury will be removed amalgam: conventional amalgams and non-ɣ2-amal-
in the oral cavity when the mix is squeezed/packed gams. Copper amalgam is included in the background
into the prepared tooth cavity. This squeezing description to clarify its specific properties.
out/packing is referred to as condensation by dental
science but has nothing to do with the term as used in Conventional amalgams
physics. The wet technique requires the use of bulk
mercury and alloy. As a consequence of the ban on Due to the fact that the alloy of conventional
the use of bulk mercury in dentistry agreed upon in amalgams contains max. 6% copper, they are also
the Minamata Convention, this technique will be known as low copper amalgams. These are rich in the
prohibited in the future. However, many manufac- ɣ2-phase, known for its poor corrosion resistance
turers still provide bulk alloy and mercury. One (Anusavice et al. 2012).
manufacturer gives two alternative mixing ratios, 1:1 ISO 1559, 1st ed. 1978 (now withdrawn), stated:
and 1:1.2, the latter suitable for dentists preferring the
Silver: 65% min.
wet technique (Nordiska Dental 2017).
Tin: 29% max.
Study of the microstructure of the amalgam filling
Copper: 6% max.
reveals that it is not homogenous, but it consists of a
Mercury: 3% max.
number of different phases; ɣ1, ɣ2, ɛ and more
Zinc: 2% max.
(Anusavice et al. 2012). Depending on the copper
content, the fillings are termed either low copper
amalgams or high copper amalgams. These expres- Non-ɣ2-amalgams
sions refer to the now withdrawn standards ISO 1559
Ed.1 and Ed.2, which stipulated 6% Cu max. and The first one of these non-ɣ2-amalgams was patented
30% Cu max., respectively. When increasing the by a Canadian inventor (Youdelis 1967). It later
copper content, the ɣ2-phase slowly disappears and at became known as Dispersalloy and its alloy partly
around 12%, it has almost disappeared. Amalgams contains particles with a spherical form. This spher-
with a copper content resulting in no ɣ2-phase are ical alloy for dental applications, used in many of
called non-ɣ2 amalgams (non-gamma-two). today’s mercury fillings, was invented by the Amer-
The ɣ1-phase, present in both low and high copper ican Dental Association (Marjenhoff and George
amalgams, is transformed to the β1-phase with 1992). Grantees of the US Public Health Service was

123
Biometals

not allowed to protect their inventions before 1980, amalgam are placed in a spoon and heated over an
so the ADA never had the opportunity to patent it. open flame until droplets of mercury are visible on
These new amalgams were initially not in accor- the surface of the metal, see Fig. 1.
dance with the standard above, so ISO 1559 Ed. 2, The tablets are then crushed and triturated with
1986 (now withdrawn), was released updating the pestle and mortar and allowed to cool and is then
composition requirements to include alloys with high inserted into the prepared cavity. In the Nordic
copper contents that already had been on the market countries, it was predominantly used in children with
for more than 10 years: extensive caries, but was sometimes also used in
adults. The latest documented use in Sweden is from
Silver: 40% min.
1981 and in Norway it was used as late as 1994
Tin: 32% max.
(Kromberg and Röynesdal 1994). It was sold in
Copper: 30% max.
Europe as late as 2001 (Produits Dentaires SA 2001).
Mercury: 3% max.
Copper amalgam is known for its high corrosion
Zinc: 2% max.
rate, giving it increased antibacterial effects (Örstavik
The present standard is ISO 24234 Ed.2, 2015, and 1985). In a document from the Nordic Institute of
includes other compositions, which have been on the Dental Materials (NIOM), the head of the institute
market in violation of ISO 1559 Ed.2: calculates that a child with copper amalgams in all
molars (10 g) could be exposed to 2.3 g of mercury
Silver: 40% min.
and 1.0 g of copper annually in a worst case scenario
Tin: 32% max.
(Mjör 1981).
Copper: 30% max.
Copper amalgam is still sold in India and the
Indium: 5% max.
provider is also an exporter (Pyrax Polymars 2017).
Palladium: 1% max.
Even though its use may be limited, it is still regarded
Platinum: 1% max.
as a viable alternative by the Indian Dental Academy,
Zinc: 2% max.
a national leader in continuing dental education
Mercury: 3% max.
(Indian Dental Academy 2017). It is not mentioned
The mercury in the alloy standards above is there in the Minamata Convention despite the fact that the
to allow for pre-amalgamation to aid the final mixing, use of copper amalgam is one of the few activities
the trituration, with mercury. apart from Artisanal and Small-Scale Gold Mining
ISO standards do not regulate the market for (ASGM), where mercury is deliberately heated with
mercury fillings but products already on the market extensive emission of mercury as a consequence.
drive the development of these standards. The Indian company confirms that it sells copper
amalgam with approx. 70% mercury in the form of
Copper amalgam

One outdated member of the family of mercury


containing filling materials is the copper amalgam. It
must not be mistaken for the low or high copper
versions mentioned above.
Copper amalgam is provided as small round or
square tablets consisting of approx. 70% mercury and
approx. 30% copper. Sometimes it is spiked with
approx. 1% of cadmium (Örstavik 1985). Cadmium
amalgam with cadmium and tin has been in use. It
was discontinued when found that cadmium was one
of the worst metals that could be used in a dental
alloy and therefore already in 1849 recommended to
Fig. 1 Two tablets of copper amalgam in a spoon heated over
not use (Hodgen 1924). When restoring a dental an open flame ready to be crushed. With courtesy of the
cavity with copper amalgam, small pieces of Norwegian TV Company NRK

123
Biometals

tablets to be heated. In the package insert, it is One of the very few pictures of these droplets in
however stated that the tablets consist of equal the dental scientific literature can be seen in one of
amounts of mercury and copper. If the latter is true, the big standard encyclopedias of dental materials
this is a new dental alloy not previously accounted for accompanied by the text: “The small, very light,
in the scientific literature (Pyrax Polymars 2017). drop-shaped areas on particle phase are high in
mercury owing to the freshly polished specimen
(91000).” (Anusavice et al. 2012). No further
Instability phenomena discussion of the phenomenon is offered. Another
picture of droplets without comment is presented by
Droplets on the surface of non-ɣ2-amalgams Herö et al. (1983).
A few papers, published outside of the dental
Polishing the surface of many high copper amalgams community, have however dealt with this phe-
stimulates the formation of droplets rich in mercury, nomenon. Both the formation of droplets and
see Figs. 2 and 3. This formation happens even if the documentation of them is presented by a corrosion
polishing takes place under cold water to avoid any expert, outside of the dental community (Pleva 1994).
rise in temperature and continues a number of hours In another study, the investigator has indeed seen
after the polishing has stopped. small “globules” on all surfaces of fillings from
This phenomenon was first described by Rehberg extracted teeth, indicating that this is not just an
and Scharschmidt in 1976 and has since been verified in vitro phenomenon but indeed occurs in clinical
by a number of researchers (Rupp et al. 1979; situations. Unfortunately the type of amalgam was
Schneider and Sarkar 1982; Sarkar et al. 1991). not accounted for (Fredin 1994).
Publication has mainly been done in the form of In 1985, one of the authors (UB) contacted the
scientific meetings abstracts but to our knowledge no National Board of Health and Welfare in Sweden
dental scientific journal paper has ever been devoted about findings of droplets on the surface of modern
to this most striking phenomenon alone. Some amalgams. The Swedish Institute for Metals Research
abstracts are not even possible to get from the dental was given the task of stripping these small droplets
organization, who initially held the meetings. How- from the surface to determine their content of
ever, there has obviously been internal discussions mercury. Through an extraction replica technique,
taking place and some regard this as a polishing five droplets were lifted from the surface and
artefact. Observations of droplets have however been measurements ranged from 44.1 to 85.4% mercury
made on clinical fillings contradicting this notion (Lehtinen 1985).
(Fredin 1994). These findings gave rise to the suspicion that the
formation of these droplets was accompanied by an
increased emission of mercury vapor. A final exam-
ination project was initiated at Linköping University
to study mercury vapor emission in amalgams,
previously found to produce droplets, with low
copper amalgams used as controls. It was concluded
that, indeed, non-ɣ2 amalgams exhibit an increased
emission of mercury vapor (Toomväli 1988).
One would expect that droplets rich in mercury
found on high copper fillings should have been
published and discussed in journals commonly read
by dental personnel, especially in an issue involving
safety. As far as we can find, this has not happened.
This is one of two phenomena of instability,
introduced with the new non-ɣ2-amalgams. The other
Fig. 2 Droplets of mercury on the surface of modern, high
copper non-ɣ2-amalgam, photographed with a light micro- is described below.
scope (9252 magnifying). Photo: Ulf Bengtsson

123
Biometals

Fig. 3 A sphere of mercury on the surface of modern, high copper non-ɣ2-amalgam, documented with a scanning electron
microscope (SEM). Note the strong signal from mercury as the electron beam passes the sphere. Photo: Ulf Bengtsson

Fig. 4 Mercury vapour loss 1200


ART

(ng) between 0.5 and


30 min after abrasion. Left
group (red cross-hatched 1000
bars): non-ɣ2-amalgams;
IDP

third bar from right (blue 800


hatched): reduced ɣ2-
amalgam; right group (two
white bars): old, 600
conventional ɣ2–containing
amalgams Diagram based
400
IND

SYB
DIS

on findings in Mahler et al.


(1994). (Color
VAL

TYT
PH

figure online) 200


OII

ONZ
OPT

Increased emission of mercury vapor in non-ɣ2- 1970s, see Fig. 4. Using the highest emitter of the low
amalgams copper amalgams as a baseline, the high copper
amalgams emits 3–43 times as much mercury vapor
In 1994, it was shown that the amount of tin in the depending on brand. One of the most wide spread
ɣ1-phase is related to the emission of mercury vapor amalgams, DIS, emits ten times the amount of
(Mahler et al. 1994). Based on this paper, it is mercury vapor as compared with the highest emitter
possible to identify the brands tested: conventional of the conventional amalgams, OPT, under the
amalgams, amalgams with reduced amount of ɣ2- experimental conditions used.
and non-ɣ2-amalgams. The result is clear; non-ɣ2- Also Ferracane (1995) compared losses of mercury
amalgams emit substantially more mercury vapor as related to the amount of ɣ1-phase. He confirmed
than the old, conventional ones used before the the pattern of differences in mercury vaporization

123
Biometals

from amalgams of different composition. Using the Conclusion


highest emitter of the low copper amalgams as a
baseline, the high copper amalgams emitted 3–62 The non-ɣ2-amalgams are marketed as superior in
times as much mercury vapor depending on brand strength and corrosion resistance. When trying to
and the high copper amalgams had by far the highest meet these goals for development, a strong sub-
emission of mercury vapor (Ferracane 1995). optimization has occurred. In experimental set ups,
In an investigation measuring differences in mer- these amalgams, being introduced in the 1970s, emit
cury vapor emission in corroded and uncorroded about ten times more mercury vapor than the ones
samples, only one non-ɣ2-amalgam and one low previously used. Ordinary dental personnel, politi-
copper amalgam was used. The pattern is once again cians and other decision makers has not been
confirmed with the non-ɣ2-amalgam emitting sub- informed about the instability of modern non-ɣ2-
stantially more mercury vapor than the conventional amalgams.
one (Boyer 1988). Corroded samples emitted more
mercury vapor than not corroded ones (Boyer Acknowledgements This research did not receive any
specific grant from funding agencies in the public,
1988). In another investigation, using the same commercial, or not-for-profit sectors.
brands of amalgam as Mahler et al. (1994), the
specimens were abraded, immersed in artificial saliva Compliance with ethical standards
and mercury was then measured in the solution after
Conflict of interest The authors have no conflicting interests.
2h (Marek 1997). Also in this investigation, the
mercury loss decreased with increasing tin content in Open Access This article is distributed under the terms of the
the ɣ1-phase. In a second part of the test, when the Creative Commons Attribution 4.0 International License (
specimens were treated differently in order to gen- http://creativecommons.org/licenses/by/4.0/), which permits
erate an oxide layer before testing, there was no unrestricted use, distribution, and reproduction in any medium,
provided you give appropriate credit to the original author(s)
relation between mercury loss and tin content. and the source, provide a link to the Creative Commons
In the four investigations above, the main license, and indicate if changes were made.
researchers in dental amalgam are all reaching similar
results. When the reducing oxide layer is removed,
the emission of mercury is inversely related to the
References
amount of tin in the gamma-1 phase. This oxide layer
is very fragile, so touching the surface with a piece of Anusavice KJ, Shen C, Rawls HR (2012) Phillips’ Science of
cotton wool will result in higher levels of mercury Dental Materials, 12th edn. Elsevier, St. Louis
vapor. Bergdahl G (1973) Residual mercury and amalgam quantity in
Unfortunately, we cannot find any openly pub- conventional and wet techniques. Eur J Oral Sci 81:260–
264
lished information/discussion on increased emission Boyer DB (1988) Mercury vaporization from corroded dental
of mercury vapor from modern amalgams in any amalgam. Dent Mater 4:89–93
journal commonly read by dental personnel. On the Ferracane JL (1995) Mercury vaporization from amalgams
contrary, several big national and international dental with varied alloy compositions. J Dent Res 74(7):1414–
1417
organizations have stated that mercury fillings are Fredin B (1994) Mercury release from dental amalgam fillings.
stable. Int J Risk Saf Med 4(3):197–208
Thereby, this is the second phenomenon of Herö H et al (1983) Surface degradation of amalgams in vitro
instability, introduced with the new non-ɣ2-amal- during static and cyclic loading. Scand J Dent Res
91:488–495
gams, which needs to be considered when evaluating Hodgen JD (1924) Practical dental metallurgy, 6th edn. Mosby,
exposure and losses of mercury from dental amal- Maryland Heights
gam. Increased emission of mercury vapor may be Homme KG et al (2014) New science challenges old notion
provoked by a slight touch of the filling surface as by that mercury dental amalgam is safe. Biometals 27(1):19–
24. doi:10.1007/s10534-013-9700-9
chewing or polishing or by a slight increase of Hylander LD, Plath D (2006) Microscopy and certification as
temperature such as consuming hot beverages or hot tools for environmentally benign, mercury-free small-
food. scale gold mining. Sci Total Environ 368:371–383

123
Biometals

Indian Dental Academy (2017) Dental amalgam course by Nordiska Dental (2017) ANA 70, directions for use. Nordiska
Indian dental academy. Slide 53. Dental, Angelholm
http://www.slideshare.net/indiandentalacademy/dental- Örstavik D (1985) Antibacterial properties of and element
amalgam-rotary-endodontic-courses-by-indian-dental- release from some dental amalgam. Acta Odontol Scand
academy 43:231–239
Kromberg M, Röynesdal K (1994) Statens Helsetillsyn. Bruk Pleva J (1994) Dental mercury—a public health hazard. Rev
av kopperamalgam som tannfyllningsmateriale— Environ Health 1:1–27
tannhelsetjenstens internkontrollsystem. 94/02832 Produits Dentaires SA (2001) Copper Amalgam. Leaflet on
Lehtinen B (1985) ATEM-undersökning av amalgam. Institutet dental products, Vevey
för Metallforskning Pyrax Polymars (2017) Copper amalgam insert, Haridwar,
Mahler DB, Adey JD, Van Eysden J (1973) Transformation of Uttarakhand. http://www.pyraxpolymars.in/copper-
ɣ1 in clinical amalgam restorations. IADR Abstract 190 amalgam.htm. Accessed 15 Jan 2017
Mahler DB et al (1994) Hg emission from dental amalgam as Rupp NW et al (1979) Characterization of the surface of
related to the amount of Sn in the Ag-Hg (ɣ1) phase. copper-rich amalgams. IADR abstracts #356.
J Dent Res 73(10):1663–1668 Sarkar N et al (1991) Amalgamation reaction of Dispersalloy—
Marek M (1997) The effect of tin in the Ag-Hg phase of dental reexamined. IADR abstracts #217
amalgam on dissolution of mercury. Dent Mater 13(5– Schmalz G, Arenholt-Bindslev D (2009) Biocompatibility of
6):353–359 dental materials. Springer, Berlin
Marjenhoff WA, George LA (1992) Paffenbarger Research Schneider PE, Sarkar NK (1982) Mercury release from Dis-
Center. The cutting edge of dental science. J Am coll persalloy amalgam. IADR Abstract 630
Dent. 4:6–9 Toomväli C (1988) Linköping University. LiU-IFM-Kemi-Ex
Mjör I (1981) Kadmium i kopperamalgam. NIOM Jnr 51/8 150
Möller B (1978) Reaction of the human dental pulp to silver Youdelis WV (1967) US Patent 3305356), February 21
amalgam restorations. Swed Dent J 1:93–97

123

You might also like