Professional Documents
Culture Documents
,
Depen
, Distamine
, Pendramine
).
d. 2,3-Dimercapto-1-propanesulfonic acid (synonyms: DMPS, Unithiol).
e. Not Available.
Mercury coordination complexes and chelates will dissociate and release free mercury ions
depending upon the binding constant. The higher the binding constant, the less free mercury is
available. Note also that the binding constant is given as a logarithmic scale and each integral
increment corresponds to a factor of 10x. For example, the mercury coordination complexes
presented in Tables 2 and 3 with their relatively large binding constants would all exist
essentially in the bound form (>99.9999%) under normal or neutral pH conditions.
Mercury also forms good mixtures or alloys with other metals. Mercury alloys are most often
referred to as amalgams largely due to the fact that liquid, elemental mercury actually
dissolves and solubilizes other metals under ambient conditions thereby forming a mixture or an
amalgam of materials. The resulting mercury-metal amalgam or alloy is a solid mixture with
characteristically different materials properties than that of any of its constituent components,
analogous to bronze, steel, pewter and related metal alloys.
The structure and properties of mercury amalgams, like all alloys, are best understood in terms of
phase diagrams. Ordinarily we consider there to be three phases or states of matter: solid, liquid
and gas. In materials science, however, the solid phase is further characterized by additional
phases distinguishable by the nature and arrangement of the different atomic or metallic
components in the material or alloy.
The different phases in materials science are usually referred to and prefixed with Greek letters
and are often subscripted with Arabic numerals. For example, the -, - or -phase or the
1
-,
2
-,
and
3
-phase of an alloy or amalgam. Phases refer to and contain characteristically different
metal elemental ratios or stoichiometries (for e.g., different intermetallic components: Ag
2
Hg
3
,
Sn
7
Hg, etc.) and hence characteristically different materials properties (i.e. creep, corrosion,
etc.).
Different parts of an alloy may be richer or weaker in one phase or another. For example, dental
amalgam may have mercury-rich phases (for e.g., Ag
2
Hg
3
) in the interior or in the bulk of the
amalgam material and mercury-poor phases (for e.g., Sn
7
Hg) at the solid-air or solid-liquid
interface, i.e. at the surface of the amalgam material. The bulk macroscopic materials properties
as well as the surface properties of amalgams and alloys depends upon the disposition and
structure of the alloy at the molecular level (i.e., its phase composition).
14
The structure and disposition of the phases of a particular alloy or amalgam will be highly
dependent upon the initial concentration of materials, i.e. the nature and quantity of the
individual metallic components, as well as the conditions in which the alloy or amalgam is
formed or prepared.
Mercurys ability to form relatively stable metal alloys or amalgams with unique materials
properties is the basis for its use as a restorative or filler in dentistry.
Environmental Chemistry
The conversion of ionic mercury or dissolved mercury into mercuric sulfide (HgS) has
historically been considered an important means of sequestering mercury in the environment. For
all practical purposes HgS displays no finite or measurable solubility in water under typical
environmental conditions. The aqueous solubility product constant for mercuric sulfide is
approximately 10
-32
(i.e., K
sp
(HgS)
1 x 10
-32
):
HgS
(solid)
Hg
+2
(aq.)
+ S
-2
(aq.)
K
eq
= K
sp
= [Hg
+2
][S
-2
] 1 x 10
-32
In other words, the dissolved mercury concentration in aqueous solution resulting from the
dissolution of solid HgS is about 2x10
-8
ppb (parts per billion) or 20 parts per quintillion.
Solid HgS can, however, exist as extremely small particles and as colloidal materials ranging in
size from about 100 (Angstroms) or less, which makes them relatively difficult to remove by
conventional filtration processes. These colloidal particles are very transportable in the
environment, and, as extremely small particles, they are readily accessible to redox chemistry
(chemical reduction-oxidation reactions). Mercuric oxide (HgO) can also undergo redox
chemistry.
Under the appropriate conditions, redox reactions can solubilize the mercury contained in HgS
and therefore release additional mercury into the environment. One mechanism of action is
thought to be an oxidation of the sulfide (ultimately to the sulfate), in combination with or in the
absence of light, with concomitant release of mercury ions:
HgS HgSO
4
Hg
+2
(aq.)
+ SO
4
-2
(aq.)
HgS undergoes oxidation reactions, particularly in the presence of light (sunlight) as well as in
the presence of chemical agents or reagents.
Increasingly more evidence is suggesting that HgS may not play as a benign role in the biosphere
as originally thought, i.e. HgS may not be completely sequestered in the environment. Both HgS
redox chemistry and the binding of HgS to DOM (Dissolved Organic Matter) can remobilize
mercury into the environment. DOM in aquatic systems, for example the humic acids, fulvic
acids and related materials, is known to bind metals and affect their speciation, transport and role
in the environment. Recent studies have demonstrated that dissolved organic matter solubilizes
HgS, even in sulfidic environments.
15
There are a relatively large number of mercury compounds- both natural and synthetic. However,
in the ecosystem, the most important and biologically active mercury species are elemental
mercury (Hg
0
), ionic mercury (Hg
2
+2
and Hg
+2
), mercuric sulfide (HgS), and organic mercury,
particularly monomethylmercury (CH
3
-Hg
+
).
Mercuric sulfide (HgS) was once considered essentially non-labile and was considered a
chemical sink (once formed, it is precipitated and essentially removed from the mercury
cycle). However there is increasing evidence that HgS may be remobilized into the environment.
The primary labile forms of mercury found in the environment, originating from either natural or
synthetic sources, include Hg
0
, Hg
2
+2
, Hg
+2
, CH
3
-Hg
+
and CH
3
-Hg-CH
3
:
Hg
0
Hg
+1
Hg
+2
CH
3
-Hg
+
CH
3
-Hg-CH
3
The mercurous ion Hg
2
+2
readily oxidizes to Hg
+2
or disproportionates to Hg
+2
and Hg
0
under
most environmental conditions therefore the chemistry and physiology of Hg
2
+2
is essentially that
of Hg
0
and Hg
+2
.
Hg
2
+2
Hg
+2
+ Hg
0
In contrast to biological speciation, the different mercury compounds that exist in the
environment, naturally or from anthropogenic sources, is often referred to as chemical
speciation.
Mercury chemical speciation is a relatively facile transformation that readily and routinely
occurs in the biosphere. The important biologically active Hg
0
, Hg
2
+2
, Hg
+2
, and methylmercury
species readily interconvert in vivo and in vitro.
Energetically speaking, the free energies (G) associated with chemical bond breaking and
chemical bond formation (and chemical reduction-oxidation or redox reactions) for the different
mercury species are all well within the realm of the accessible energetics available in the
biosphere.
Multiple chemical reaction pathways exist for the interconversion of the different mercury
species in vivo- through the biochemical action of enzymes and microorganisms, as well as in
vitro- through the chemical action of the elements: air (oxygen), light (photochemistry) and
water (hydrolysis).
For example, the following chemical and biochemical transformations readily occur in the
biosphere:
Hg
0
+ air + sunlight Hg
+2
Hg
0
+ catalase (enzymatically) Hg
+2
Hg
+2
+ microbially (reductase) Hg
0
16
Hg
+2
+ microorganisms CH
3
-Hg
+
CH
3
-Hg
+
+ microorganisms (methanogens) Hg
0
+ CH
4
CH
3
-Hg
+
+ H
+
+ microbially (lyase) Hg
0
+ CH
4
Sulfate Reducing Bacteria H
2
S H
2
S + Hg
+2
HgS + Hg
2
S
HgS + Thiobacillus spp. H
2
S + Hg
+2
The inherent nature of the chemical bonding of mercury compounds is ultimately responsible for
their unique properties and reactivities. These properties and reactivites are, in turn, reflected in
their transport, partition, and distribution in the environment as well as in their transport,
partition, and distribution in living organisms (mammal, bird, fish, etc.).
U.S. Mercury Use and Emissions
Mercury Use
According to the U.S. Geological Survey (USGS), overall mercury consumption in the U.S. has
decreased significantly since the early 1980s. Regulatory efforts and concerns regarding the
environmental fate of mercury-containing products have been steadily driving mercury
consumption downward.
In 1997, the single largest domestic use of mercury was in the chlor-alkali process, i.e. the
electrolytic generation of chlorine (Cl
2
) and caustic soda (NaOH) from aqueous brine (NaCl)
solutions:
2NaCl (aq.) + 2H
2
O H
2
(g) + Cl
2
(g) + 2NaOH (aq.)
The electrochemical cell used to carry out the electrolysis reaction employs mercury as the
electrode.
Table 1 summarizes the major uses of mercury in the U.S. and Figure 1 graphically depicts
relative U.S. consumption of mercury depending upon source or category.
Table 1. U.S. Domestic Mercury Consumption
a
Mercury Source Amount
b
(tons)
Chlorine & Caustic Manufacture
c
160
Electrical: Wiring Devices & Switches 57
Dental Amalgam 40
Electric Lighting 29
Instruments: Measuring & Control 24
Other
d
36
346 tons Total
17
a. U.S. Geological Survey (USGS) estimates; taken from the USGS 1997 Minerals Yearbook.
b. For 1997, the last year the USGS provided mercury consumption data.
c. Chlor-Alkali Industry.
d. Other uses include mercury used in chemicals, batteries and laboratory instruments; amounts
used in these other categories are often withheld to avoid disclosing company proprietary
information.
U.S. Mercury Consumption
Other
10.4%
Lighting
8.4%
Dental
11.6%
Electrical
16.5%
Chlor-Alkali
46.2%
Instruments
6.9%
Figure 1. U.S. Mercury Use (1997, USGS).
The chlor-alkali industry, the single largest consumer of mercury, has voluntarily committed to a
50% reduction of mercury use by 2005. The chlor-alkali industrys annual disclosure to the EPA
reports a usage of 107 tons of mercury in 1999, down from 160 tons in 1997. It appears that the
chlor-alkali industry is well on its way to meeting its mercury reduction goal.
Mercury use in the U.S. has dropped from 2,033 tons in 1980 to 346 tons in 1997, a decline of
about 83%. According to the USGS, mercury use continues to decline in all categories except in
dental use and lighting. Mercury usage in the dental industry appears to remain steady at about
40-50 tons per year. Domestic mercury consumption for 2001 is estimated to be about 220 tons,
of which dental amalgam usage is estimated to be about 48 tons. Although mercury consumption
for the dental industry has remained relatively constant, its percentage of the total has increased
from about 2% in 1980 to about 22% in 2001.
Mercury Emissions
There has been no increase or decrease in the total amount of mercury on planet earth since it
was formed over 4 billion years ago. Extraterrestrial sources of mercury or entry of mercury into
the earths sphere from outer space (for e.g., meteorites) and planetary loss of mercury from the
earth out-gassing remain negligible contributors to the overall amount of mercury on planet
earth.
18
In contrast, the amount of mercury available to circulate within the environment has increased
continually since the beginning of the industrial age. The increasing pace of global
industrialization is predicting an increasing amount of mercury emissions into the environment
from anthropogenic sources.
Both natural and human activities give rise to an increased cycling of mercury into the
environment. Presently, it is estimated that about 60% of the global emissions of mercury into
the atmosphere comes from anthropogenic sources and the remaining 40% from natural sources.
Natural sources of mercury include volcanoes, geologic or mineral deposits and volatilization or
evaporation from the earths oceans.
The focus of the present account is on mercury emissions into the environment from
anthropogenic or human related activities. It is these anthropogenic sources of mercury that are
causing an increase in the levels of mercury in the biosphere above that of their natural or
background levels.
Mercury and mercury emissions into the environment have been studied by many international
and national organizations. Global mercury studies include studies conducted by the United
Nations Environment Programme (UNEP) and the World Health Organization (WHO). In the
United States, the Environmental Protection Agency (EPA) and the Department of Energy
(DOE) have conducted the most studies concerning mercury emissions, particularly emissions
into the atmosphere. Other U.S. government organizations studying mercury and its emissions
include the National Science Foundation (NSF), the U.S. Geological Survey (USGS), the
General Accounting Office (GAO) and several other state and local organizations.
Table 2 summarizes the primary sources of mercury emissions in the United States for 1994-
1995, years in which there is sufficient data. The major human activity contributing to
anthropogenically-emitted mercury is that from the burning of fossil fuels and waste (>88%).
Table 2. U.S. Annual Anthropogenic Mercury Emissions
a
Mercury Source Amount
b
(tons/year)
Major Sources:
Coal Burning Utility Plants 52.0
Boilers: 32.1
Commercial 28.8
Residential 3.3
Municipal Waste Combustors 29.6
Medical Waste Incinerators 16.0
Other Sources:
Hazardous Waste Combustors 7.1
Chlor-Alkali Industry 6.5
Portland Cement 4.4
Lamp Breakage 3.1
Pulp & Paper Industry 1.7
General Laboratory 1.4
Dental Preparations 0.6
19
Total 154.5 tons/year
a. Environmental Protection Agency.
b. Given in tons per year, 1994-1995.
The largest single contributor to U.S. mercury emissions is that from coal-fired utilities (33.7%).
Figure 2 depicts a graphical overview of annual mercury emissions in the United States based on
the relative contribution of the different anthropogenic or human-derived activities.
U.S. Mercury Emissions
Dental
0.4%
Pulp & Paper
1.1%
General Lab
0.9%
Coal Utilities
33.7%
Muni Waste
19.2%
Boilers
20.7%
Haz Waste
4.6%
Portland Cement
2.8%
Med Waste
10.3% Lamp Breakage
2.0%
Chlor-Alkali
4.2% Other
16.0%
Figure 2. Annual U.S. Emissions of Mercury into the Environment (EPA).
Mercury released from the burning of fossil fuels is actually natural mercury which was once
sequestered but is volatilized and mobilized into the environment as a result of the fuel burning
or combustion process. Mercury exists naturally in varying concentrations in all fossil fuels. The
largest concentrations of mercury are found in coal, with amounts that are highly dependent upon
the type of coal (for e.g., anthracite, bituminous, etc.). Lesser amounts of mercury occur
naturally in petroleum and even smaller amounts are found in natural gas.
Mercury released from incinerators and combustors is generally from unnatural sources or from
products of manufacture such as batteries, paints, fluorescent lamps and the incineration of
medical, hazardous and sludge wastes.
At first glance, it appears that mercury from dental sources contributes an insignificant amount
of mercury cycling into the environment; however, mercury originating from dental sources is
also included in the municipal and medical waste incineration category and may also be included
in the hazardous waste category. Estimates from the present account suggest that dental mercury
emissions may contribute from 4% to 19% to the overall mercury emissions, significantly
20
different from published reports. Ultimately all dental mercury will end up in the environment,
the key issue is just how dispersed that mercury will be.
The results presented in Table 2 and Figure 2 are based on EPA and industry estimates. Although
these estimates are the best available estimates regarding U.S. mercury emissions, they are
fraught with a great deal of uncertainty. In many instances the reported values are based on
indirect measurements or rely on additional underlying estimates and assumptions.
Reported mercury emissions may be largely underestimating the actual amounts of mercury
discharged annually into the environment. In a later section, we assess and comment on these
emission estimates, particularly as they pertain to mercury emissions from the dental industry.
Mercury in Dentistry
The dental operatory may encounter mercury in several forms:
(1) Elemental mercury (Hg
0
): in liquid form, which is used to form amalgams, and its vapors.
(2) Mercury amalgam and associated intermetallic mercury compounds (e.g., Ag
2
Hg
3
, Sn
2
Hg).
(3) Ionic mercury (Hg
+2
and Hg
+1
) from oxidation of mercury and its intermetallic compounds.
(4) Mercuric sulfide (HgS) from microbial action and decay.
(5) Colloidal mercury: mercury attached to biomolecules (for e.g., sulfhydryl-containing
proteins), mercury attached to inorganic substrates, and colloidal mercury amalgam particles.
Each of these different forms of mercury may enter the biosphere and exert its adverse effects on
the environment and ultimately on human health. Recognition of the hazards associated with the
handling and use of mercury in the dental operatory has led to an active search for new mercury-
free amalgams and metal-free dental composites. Mercury free or reduced amalgam alternatives
include gold and ceramic inlays, gallium alloys, and packable resin composites. However,
mercury amalgam still remains the most widely used dental filling to date.
Professionals, including scientists, dentists and physicians, are well aware of the hazardous
nature of mercury and usually exercise all of the appropriate cautions and practices when using
mercury and mercury compositions. Laboratories are statutorily required to safely use and
dispose of all toxic and hazardous chemicals including mercury and mercury compounds.
Typically, silver fillings or dental amalgam consists of about equal parts of mercury and a metal
alloy. This metal alloy, which is often referred to as dental alloy or amalgam alloy, is the dental
amalgam precursor. The dental alloy is primarily composed of silver, tin and copper and often
contains small or trace amounts of zinc and other minor metal components. It is mixed or
amalgmated with elemental mercury just prior to its use to form the dental amalgam or silver
filling.
The two materials comprising silver fillings (mercury metal and dental alloy) are physically
mixed or triturated to the consistency of a paste just prior to use and then set into place in the
tooth and allowed to harden. The placed amalgam material is shaped and any excess amalgam is
21
scraped and removed at the dental operatory. Amalgam fillings are the most widely used dental
filler materials in the world for dental carries or cavities.
A good deal of control over the variation of the metal composition in the dental alloy is provided
by manufacturing standards adopted by professional dental organizations and manufacturers of
dental materials. Table 1 lists the more common standards for dental alloys. In addition to the
alloy metal compositions shown in Table 1, manufacturers or professional organizations provide
standard instructions for the proportions of mercury and alloy to be mixed for final
amalgamation to form the silver filling.
Mercury for dental use is always composed of high purity elemental mercury. The European and
International standards for dental mercury, i.e., EN 21560 (1991) and ISO 1560 (1985),
respectively, are identical and require dental mercury purity to be greater than or equal to
99.99% elemental mercury (Hg).
There is a great deal of compositional flexibility regarding the amalgam standards which have
been adopted by professional organizations (note the ANSI/ADA standards in Table 1 footnotes
f, g, h and i). This compositional flexibility is due primarily to the fact that standard
specifications regarding amalgams need to address the materials properties of the alloy or filling,
namely its compressive strength, dimensional stability, and creep. Satisfying these physical
properties specifications confers a great deal of flexibility regarding the amalgam metal
composition.
Table 1. Standards for Dental Alloy Compositions
a
EN 21559
b
ISO 1559
c
ANSI/ADA
d
Silver (Ag) 40% (min.) 40% (min.) f
Tin (Sn) 32% (max.) 32% (max.) f
Copper (Cu) 30% (max.) 30% (max.) g
Zinc (Zn) 2% (max.) 2% (max.) g, i
Mercury (Hg) 3% (max.) 3% (max.) g
Indium (In) ----
e
5% (max.) h
Palladium (Pd) ----
e
1% (max.) h
Platinum (Pt) ----
e
1% (max.) h
a. min.= minimum concentration (%, by wt.); max.= maximum concentration (%, by wt.). The composition or purity
of the dental mercury used in amalgamating the dental alloy to form the silver filling is given in EN 21560 (1991)
and ISO 1560 (1985), which are identical: greater than or equal to 99.99% elemental mercury (Hg).
b. European standards or European Norms: EN 21559 (1991).
c. International Organization of Standards: ISO 1559 (1995).
d. ANSI: American National Standard Institute; ADA: American Dental Association.
e. No standards currently available for these metals.
f. According to ANSI/ADA Specification No. 1 (1979), Reaffirmed (1993), The chemical composition shall consist
essentially of silver and tin.
g. Further to ANSI/ADA Specification No. 1 (1979), Reaffirmed (1993), Copper, Zinc, gold, and/or mercury may
be present in amounts less than the silver and tin content.
h. Further to ANSI/ADA Specification No. 1 (1979), Reaffirmed (1993), Other elements may be included provided
the manufacturer submits the composition of the alloy and the results of adequate clinical and biological
22
investigations to the Council on Dental Materials and Devices, American Dental Association, to show that the alloy
is safe to use in the mouth as directed in the manufacturers instructions.
i. . Further to ANSI/ADA Specification No. 1 (1979), Reaffirmed (1993), Alloys containing zinc in excess of
0.01% shall be described as zinc-containing. Those alloys containing zinc equal to or less than 0.01% shall be
designated as nonzinc.
There are many commercially available dental alloys with varying metal compositions which all
satisfy the appropriate EN, ISO or ANSI/ADA standards regarding compositional and materials
properties specifications. Table 2 lists the metal compositions of some of the more common
brands of dental alloys and amalgams commercially available to the dental operatory or practice.
Table 2. Composition of Some Commercially Available Dental Alloys and Amalgams
a
Brand Name Source
d
Amalgam
Composition
k
Dental Alloy Composition
c
Alloy:Hg
j
% Hg
b
% Ag % Sn % Cu Other (%)
e
AC 70 DMG 1.0 : 1.06 51.5% 69.3% 19.4% 10.9% Zn (0.4%)
Advance
TM (i)
SS White 1.0 : 1.0 50.0% 44.5% 30.0% 25.5% None
Alldent
(q)
Alldent 1.0 : 1.0 50.0% 44.0% 29.75% 25.0% Hg (1.25%)
ANA 70
m
Nordiska 1.0 : 1.0 50.0% 69.3% 19.4% 10.9% Zn (0.4%)
ANA 90 Nordiska 1.0 : 1.0 50.0% 48.0% 28.7% 21.3% Hg (2.0%)
ANA 2000
n
Nordiska 1.0 : 1.0 50.0% 43.0% 29.6% 25.4% Hg (2.0%)
ANA 3000 Nordiska 1.0 : 1.0 50.0% 51.0% 29.0% 20.0% None
Amalcap F
u
Vivadent 1.0 : 0.93 48.2% 71.0% 26.0% 30.0% None
Amalcap Plus
u
Vivadent 1.0 : 1.0
w
50.0%
w
70.1% 18.0% 11.9% None
Amalcap SAS
u
Vivadent 1.0 : 0.91 47.6% 70.1% 18.0% 11.9% None
Ardent Futura
u
Ardent 1.0 : 1.0 50.0% 44.5% 30.0% 25.5% None
Ardent High Silver
x
Ardent 1.0 : 0.9 47.4% 68.0% 27.0% 5.0% None
Ardent NG-2 70
u
Ardent 1.0 : 1.0 50.0% 70.0% 18.0% 12.0% None
Aristaloy Goldsmith 1.0 : 1.0 50.0% 68.4% 26.7% 4.3% Zn (0.6%)
Aristaloy 21 Goldsmith 1.0 : 1.0 50.0% 45.0% 31.0% 24.0% None
Artalloy Degussa 1.0 : 1.0 50.0% 80.0% 7.0% 13.0% None
Blend-A-Dispers P&G 1.0 : 1.2 54.5% 70.0% 18.0% 12.0% None
Cavex Avalloy
y
Cavex 1.0 : 1.03 50.7% 45.0% 30.5% 24.0% Zn (0.5%)
Cavex NonGamma-2
y
Cavex 1.0 : 1.07 51.7% 69.2% 18.6% 11.9% Zn (0.3%)
Cavex Octight
y
Cavex 1.0 : 0.73 42.2% 60.0% 28.0% 12.0% None
Cavex Result
y
Cavex 1.0 : 1.07 51.7% 69.2% 18.6% 11.9% Zn (0.3%)
Contour
TM
Kerr 1.0 : 0.89 47.0% 41.0% 31.0% 28.0% None
Dauerkapsel F J&J 1.0 : 1.0 50.0% 69.5% 17.7% 11.8% Hg (1.0%), Zn (1.0%)
Dentalloy
TM (h)
SS White 1.0 : 1.3 56.5% 70.5% 25.9% 2.6% Zn (<1%)
Dentina 68 F Dentina 1.0 : 1.4 58.3% 68.0% 26.0% 5.3% Zn (0.7%)
Dentina 70
t
Dentina 1.0 : 1.2 54.5% 70.0% 18.5% 11.0% Zn (0.5%)
Dispersalloy