Mercury
Entry into the marine environment
Mercury is a metal which is liquid at normal temperatures
and pressures. It forms salts in two ionic states
mercury (I) and mercury (II). Mercury (II), or mercuric,
salts are very much more common than mercury (I)
salts. Mercury also forms organometallic compounds,
some of which have found industrial and agricultural
use. These organometallic compounds are stable,
although some are readily broken down by living
organisms, while others are not readily biodegraded.
A number of reviews (e.g. WHO 1989 and 1991 and
CCME 1992, US EPA 1984) reviewed the environmental
fate and behaviour and aquatic toxicity of mercury.
These are discussed below. The reader is referred
to the above reports for a more comprehensive assessment.
Natural mercury arises from the degassing of the
Earth's crust through volcanic gases and, probably,
by evaporation from the oceans. Local levels in
water derived from mercury ores may also be high
(up to 80 µg l-1). Atmospheric
pollution from industrial production is probably
low, but pollution of water by mine tailings is
significant. The burning of fossil fuels is a source
of mercury. The chloralkali industry and, previously,
the wood pulping industry, also released significant
amounts of mercury. Although the use of mercury
is decreasing, high concentrations of the metal
are still present in sediments associated with the
industrial applications of mercury. Some mercury
compounds have been used in agriculture, principally
as fungicides.
Recorded levels in the marine
environment
WHO (1989) stated that for the open ocean and for
coastal sea-water, concentrations of dissolved mercury
in the range of 0.5 - 3 ng l-1 and
2 - 15 ng l-1 respectively could
be considered to be representative.
However, local variations from these values are
considerable, especially in coastal sea water and
in lakes and rivers where mercury associated with
suspended material may also contribute to the total
load or where near to anthropogenic sources, e.g.
in the vicinity of mining sites and chloralkali
plants for the industrial extraction of mercury.
However, the majority of mercury in the environment
can be considered to be natural rather than the
result of human activities.
WHO (1989 ) estimated concentrations in ocean sediments
probably lie in the range between 20 and 100 µg
kg-1.
Concentrations of mercury have been measured in
water, sediments and biota as part of the National
Monitoring Programme at sites throughout the UK
in estuaries and coastal waters (MPMMG 1998). The
results of the National Monitoring Programme are
summarised in Appendix D. MPMMG 1998 should be consulted
for further details.
These show elevated levels in some sediments. However,
with regard to the water column, the available data
suggest that concentrations of mercury in UK coastal
and estuarine waters appear unlikely to exceed relevant
quality standards derived for the protection of
saltwater life.
As an example of the recorded levels of dissolved
mercury in the marine environment, the following
concentrations have been reported by DETR (1998)
for some English estuaries (See tables below).
Minimum concentration (ng l-1) of dissolved
mercury in the water column of some English estuaries
(from DETR 1998)
|
1991
|
1992
|
1993
|
1994
|
1995
|
Tyne |
105.0
|
0.0
|
0.0
|
0.0
|
0.0
|
Wear |
|
24.0
|
0.0
|
0.0
|
0.0
|
Tees |
|
0.0
|
0.0
|
0.0
|
0.0
|
Ouse |
0.0
|
0.0
|
0.0
|
0.0
|
0.0
|
Wash |
0.0
|
0.0
|
0.0
|
0.0
|
0.0
|
Thames |
0.0
|
0.0
|
|
|
|
Tamar
|
0.0
|
0.0
|
0.0
|
0.0
|
0.0
|
Average concentration (ng l-1) of dissolved
mercury in the water column of some English estuaries
(from DETR 1998)
|
1991
|
1992
|
1993
|
1994
|
1995
|
Tyne |
105.0
|
59.8
|
87.9
|
0.0
|
24.2
|
Wear |
|
26.5
|
139.3
|
0.0
|
14.6
|
Tees |
|
63.8
|
19.9
|
0.0
|
16.2
|
Ouse |
33.3
|
28.2
|
7.6
|
21.4
|
5.0
|
Wash |
0.0
|
0.0
|
0.0
|
6.4
|
91.0
|
Thames |
12.1
|
21.0
|
|
|
|
Tamar
|
36.6
|
3.9
|
0.0
|
0.0
|
0.0
|
Maximum concentration (ng l-1) of dissolved
mercury in the water column of some English estuaries
(from DETR 1998)
|
1991
|
1992
|
1993
|
1994
|
1995
|
Tyne |
105.0
|
130.0
|
185.0
|
0.0
|
80.0
|
Wear |
|
31.0
|
565.0
|
0.0
|
60.0
|
Tees |
|
160.0
|
130.0
|
0.0
|
60.0
|
Ouse |
136.0
|
148.0
|
79.0
|
200.0
|
20.0
|
Wash |
0.0
|
0.0
|
0.0
|
24.0
|
430.0
|
Thames |
53.0
|
110.0
|
|
|
|
Tamar
|
249.0
|
39.0
|
0.0
|
0.0
|
0.0
|
|
|
|
|
|
|
Fate and behaviour in the marine
environment
Dissolved mercury has a strong affinity for organic
matter and suspended sediment and so can be expected
to be bound to these particles in the water column
and subsequently to accumulate in sediments. Campbell
et al 1986 reported a well defined increase
in dissolved mercury concentrations in a seaward
direction from the Mersey estuary. Within the estuary
where suspended material concentrations are greater,
concentrations of dissolved mercury decrease away
from a point source but increase again towards Liverpool
Bay.
Once deposited in sediments, mercury can undergo
methylation to produce methylmercury. This form
of mercury is bioavailable and is a hazard to aquatic
life.
Effects on the marine environment
Toxicity to marine organisms
An exhaustive literature review on the toxicity
of mercury to marine organisms has not been carried
out for the purposes of this profile. The information
provided in this section is taken from existing
review documents (WHO 1989, 1991, CCME 1992 and
US EPA 1994)). The most sensitive groups of organisms
have been identified.
The organic forms of mercury are generally more
toxic to aquatic organisms than the inorganic forms.
Macrophytes
Aquatic plants are affected by mercury in the water
at concentrations approaching 1 mg l-1
for inorganic mercury but at much lower concentrations
of organic mercury.
Invertebrates
Aquatic invertebrates vary greatly in their susceptibility
to mercury, with the concentration and species of
mercury, the developmental stage of the organisms,
and the temperature, salinity, water hardness, and
flow rate all affecting the sensitivity. Methylmercury
is more toxic than aryl or inorganic mercury. The
larval stage is apparently the most sensitive stage
of the organism's life cycle. Mercury toxicity increases
with temperature and decreases with water hardness.
Toxicity appears to be higher in flow-through systems
than in static systems. This effect is probably
due mostly to the actual concentration of mercury
available to the organism, which is lower in static
systems.
Levels of 1 to 10 µg l-1 normally
cause acute toxicity for the most sensitive developmental
stage of many different species of aquatic invertebrates.
Fish
Inorganic mercury is toxic to fish at low concentrations.
96-h LC50s as low as 30 µg l-1
have been reported. Organic mercury compounds are
more toxic. Toxicity is affected by temperature,
salinity, dissolved oxygen, and water hardness.
A wide variety of physiological and biochemical
abnormalities have been reported after exposure
of fish to sub-lethal concentrations of mercury,
although the environmental significance of these
effects is difficult to assess. Reproduction is
also adversely affected by mercury.
Seabirds
Fatalities and severe poisonings in birds have
been reported in association with outbreaks of human
poisoning. Methylmercury levels in fish in Japan
have caused a major problem for human health. During
these incidents, there were also reports of direct
effects of mercury on wildlife in the area. Fish
carrying methylmercury were found dead or showed
symptoms of mercury poisoning. Fish-eating and scavenging
birds were also killed (Harada, 1978). Birds found
dead in the area showed characteristic pathological
changes in the central nervous system of Minamata
disease, but no measurement of mercury content was
made (Takeuchi et al. 1957).
Birds, particularly coastal species or those eating
prey that feed in estuaries, have been affected
by mercury contamination. It has adversely affected
breeding and may have influenced population stability.
Merlins sampled in Scotland contained organochlorines
along with mercury in their eggs. Statistical analysis
of the data showed a clear inverse relationship
between mercury content of eggs and brood size;
the higher the mercury content, the less likelihood
of successful breeding. Productivity fell markedly
when mercury residues in eggs exceeded 3 mg kg-1.
Productivity (i.e. the number of young successfully
reared) showed no statistically significant relationship
with residues of other chemicals present in the
eggs. Levels of mercury were highest in birds sampled
in Orkney and Shetland, but the relationship between
mercury residue and productivity remained when these,
particularly high, residue levels were excluded
from the analysis (Newton and Haas, 1988).
The merlins were feeding on wading birds in estuaries
and this was presumed to be the source of the mercury.
A similar, but not quite significant, relationship
was found in peregrine falcons breeding near the
coast.
Sea mammals
There is some limited information on the effects
marine mammals.
Ronald et al (1977) fed harp seals on herring
dosed with methylmercuric chloride. Two animals
were used as controls, two were fed 0.25 mg kg-1
body weight per day and two fed 25.0 mg kg-1
body weight per day. Various blood parameters were
monitored and found to be unaffected by the lower
dose. The two animals on the higher dose died after
20 and 26 days of dosing. Prior to death, these
animals exhibited toxic hepatitis, uremia, and renal
failure.
Bioaccumulation
Although environmental levels can be considered
to be low, the high capacity of organisms to accumulate
mercury means that the metal is found widely in
aquatic animals and plants.
Inorganic mercury can be methylated in the environment
and the resultant methylmercury is taken up into
organisms more readily than inorganic mercury. The
speciation of mercury is of great importance in
determining the uptake of the metal from water and
soil. Much of the mercury in natural waters is strongly
bound to sediment or organic material and is unavailable
to organisms.
Aquatic invertebrates accumulate mercury to high
concentrations. Fish also take up the metal and
retain it in tissues, principally as methylmercury.
Although most of the environmental mercury to which
they are exposed is inorganic, there is a strong
indication that bacterial action leads to methylation
in aquatic systems. Elimination of methylmercury
is slow from fish (with half times in the order
of months or years) and from other aquatic organisms.
Loss of inorganic mercury is more rapid and so most
of the mercury in fish is retained in the form of
methylmercury.
Langston et al (1996) reported levels of
methylmercury bioaccumulated by a range of estuarine
algae and invertebrates in the Mersey estuary in
1995 to be between 10 (Fucus vesiculosus)
and 100 (Mytilus edulis) times higher than
sediment concentrations at the sites they were collected
from. Correlations between sediment and tissue levels
of methylmercury in the invertebrates suggest that
sediments are the prime source of the contaminant
for these animals.
Seabirds and those feeding in estuaries have also
been found to be contaminated. The form of retained
mercury in birds is more variable and depends on
species, organ, and geographical site.
Potential effects on interest
features of European marine sites
Potential effects include:
- acute toxicity in the water column to interest
features comprising macrophytes, invertebrates
and fish at concentrations of dissolved mercury
above the EQS of 0.3µg l-1
(annual average). Toxic effects below this concentration
may occur if methylmercury is present;
- inorganic mercury accumulates in sediments and
may be a hazard to sediment-dwelling organisms
at concentrations above 0.13 mg kg-1,
according to Canadian interim marine sediment
quality guidelines. Toxic effects below this concentration
may occur if methylmercury is present;
- methylmercury bioaccumulates in the food chain
and poses a hazard to fish, birds and Annex II
sea mammals.
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References
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