Lead
Entry into the marine environment
Lead is a bluish or silvery-grey soft metal. With
the exception of the nitrate, chlorate, and, to
a much lesser degree, chloride, the salts of lead
are poorly soluble in water. Lead also forms stable
organic compounds. Tetraethyllead and tetramethyllead
are used extensively as fuel additives. Both are
volatile and poorly soluble in water. Trialkyllead
compounds are formed in the environment by the breakdown
of tetraalkylleads. These trialkyl compounds are
less volatile and more readily soluble in water.
Lead is mined, most usually as the sulfide, "galena".
Hence, entry into the aquatic environment occurs
through releases (directly or through atmospheric
deposition) from the smelting and refining of lead,
the burning of petroleum fuels containing lead additives
and, to a lesser extent, the smelting of other metals
and the burning of coal and oil. Metallic lead deriving
from shotgun cartridges or used as fishing weights
is lost in the environment and often remains available
to organisms (WHO 1995).
Recorded levels in the marine
environment
Concentrations of lead 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.
Grimwood and Dixon (1997) compiled monitoring data
for lead in water, sediments and biota for marine
sites of nature conservation importance in England.
As an example of the recorded levels of dissolved
lead in the marine environment, the following concentrations
have been reported by DETR (1998) for some English
estuaries (see tables below).
Minimum concentration (µg
l-1) of dissolved lead in the water column
of some English estuaries (from DETR 1998)
|
1991
|
1992
|
1993
|
1994
|
1995
|
Tyne |
0.0
|
0.0
|
0.0
|
1.7
|
0.0
|
Wear |
16.0
|
0.0
|
0.0
|
0.0
|
0.0
|
Tees |
0.0
|
0.0
|
0.0
|
0.0
|
0.0
|
Ouse |
|
0.0
|
0.0
|
0.0
|
0.0
|
Wash |
|
0.0
|
0.0
|
0.0
|
0.0
|
Thames |
0.0
|
0.0
|
0.0
|
0.2
|
0.1
|
Tamar |
0.0
|
0.0
|
0.0
|
0.2
|
0.0
|
Average concentrations (µg
l-1) of dissolved lead in the water column
of some English estuaries (from DETR 1998)
|
1991
|
1992
|
1993
|
1994
|
1995
|
Tyne |
18.0
|
3.8
|
1.4
|
4.1
|
2.5
|
Wear |
31.0
|
2.1
|
0.4
|
0.6
|
2.0
|
Tees |
13.8
|
1.8
|
1.2
|
2.2
|
1.0
|
Ouse |
|
0.3
|
0.8
|
0.0
|
0.0
|
Wash |
|
0.0
|
0.0
|
0.0
|
0.0
|
Thames |
6.7
|
1.2
|
0.9
|
0.6
|
0.5
|
Tamar |
0.5
|
0.7
|
0.2
|
0.5
|
0.2
|
Maximum concentrations (µg
l-1) of dissolved lead in the water column
of some English estuaries (from DETR 1998)
|
1991
|
1992
|
1993
|
1994
|
1995
|
Tyne |
64.0
|
10.5
|
2.9
|
12.7
|
4.0
|
Wear |
72.0
|
6.0
|
2.0
|
3.3
|
9.0
|
Tees |
70.5
|
10.5
|
2.6
|
15.3
|
4.0
|
Ouse |
|
3.0
|
5.6
|
0.0
|
0.0
|
Wash |
|
0.0
|
0.0
|
0.0
|
0.0
|
Thames |
23.6
|
7.0
|
2.1
|
1.1
|
1.2
|
Tamar |
1.7
|
3.4
|
0.8
|
2.2
|
0.5
|
Fate and behaviour in the marine
environment
The fate and behaviour of lead in the marine environment
is complex because of the many compounds of lead
that can be found and the natural variability of
natural systems.
Much of the lead in the marine environment is strongly
adsorbed onto sediment and suspended particles,
reducing its availability to organisms. The transport
of lead in estuaries and coastal waters is therefore
closely linked with the movement of particles. The
sediments form a sink for lead in the marine environment.
Lead in true solution may be present as the hydrated
Pb2+ ion or may be complexed. However,
in view of the low solubility of most of its salts,
lead tends to precipitate out of complex solutions.
Effects on the marine environment
Toxicity to marine organisms
An exhaustive literature review on the toxicity
of lead 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 (Brown et al 1984, WHO 1995,
Grimwood and Dixon 1997). The most sensitive groups
of organisms have been identified.
In the form of simple salts, lead is acutely above
2.5 and >500 mg l-1 for marine organisms
(WHO 1995).
Lead salts are poorly soluble in water, with the
presence of other salts reducing the availability
of lead to organisms because of precipitation. Results
of toxicity tests should be treated with caution
unless dissolved lead is measured.
In 1984, Brown et al reviewed data on the
toxicity of lead to marine organisms and proposed
an EQS (for the protection of saltwater life) of
25 µg l-1, (expressed as a
dissolved annual average concentration), a value
currently adopted in UK legislation (HMSO 1989).
The EQS was proposed at this level as, at the time
of writing (1984), adverse effects had not been
observed in any saltwater organisms following exposure
to concentrations below 100 µg l-1.
However, following a review of more recent toxicity
data in 1992, Young (1992) proposed a more stringent
EQS of 10 µg l-1. This value
(also expressed a dissolved annual average) was
derived by applying an arbitrary safety factor of
around 2 to the lowest, most reliable No-Observed
Effect Concentration (NOEC) for mysid shrimp.
An additional review by Grimwood and Dixon in 1997
of data on the saltwater toxicity of lead available
since the EQS of 10 µg l-1
was proposed, found that only one study had been
reported that perhaps indicated higher toxicity
to saltwater organisms. Fernandez-Leborans and Novillo
(1992) reported that lead concentrations ranging
from 1 to 50 µg l-1 caused
significant effects on the division and biomass
of ciliate communities in laboratory microcosms.
However, the magnitude of effects at the 1 µg
l-1 exposure level was not distinguished
from the effects that occurred following exposure
to 50 µg l-1. Moreover, it
is difficult to assess the relevance of these laboratory
sub-lethal (growth) data in predicting wider ecosystem
effects under field conditions.
Grimwood and Dixon (1997) concluded that no other
relevant ecotoxicity data had been reported that
suggested a need to revise to the latest proposed
EQS value.
The authors recommended that the revised EQS of
10 µg l-1 (dissolved annual
average) proposed to DETR was appropriate for the
protection of all saltwater life in the majority
of cases. However, where there is concern that the
health of communities at sites of nature conservation
interest may be compromised as a result of the presence
of particularly sensitive algal or ciliate species,
a lower value may be used as a Guideline. For instance,
a value of 0.5 µg l-1 may be
used where necessary by applying arbitrary factors
of 10 and 2 to the lowest algal EC50 and the lowest
ciliate effect concentration respectively. In the
absence of any reliable supporting data, it was
not possible to confirm the precision of this value.
Algae
In one laboratory study, a 12 day EC50 (growth)
as low as 5 µg l-1 was reported
for the diatom Skeletonema costatum although
the reliability of this result is questionable due
to uncertainties in measurements and apparent medium-dependent
effects. All other algal data were higher than the
NOEC reported for the mysid shrimp. Nevertheless,
Young (1992) still concluded that, on the basis
of the potential higher sensitivity of some algae,
a more stringent standard may be required where
lead-sensitive algal species were important primary
producers in a saltwater ecosystem. Further research
into algal sensitivity was recommended.
Invertebrates
In aquatic invertebrates communities, some populations
are more sensitive than others and community structure
may be adversely affected by lead contamination.
However, invertebrate populations from polluted
areas can show more tolerance to lead than those
from non-polluted areas. In other aquatic invertebrates,
adaptation to hypoxic conditions can be hindered
by high lead concentrations (WHO 1995).
Young (1992) reported a No Observed Effect Concentration
(NOEC) of 17 µg l-1, for the
mysid shrimp Mysidopsis bahia following 44
days exposure.
Fish
Young stages of fish are more susceptible to lead
than adults or eggs. Typical symptoms of lead toxicity
include spinal deformity and blackening of the caudal
region. The maximum acceptable toxicant limit (MATC)
for inorganic lead has been determined for several
species under different conditions and results range
from 0.04 mg l-1 to 0.198 mg l-1.
The acute toxicity of lead is highly dependent on
the presence of other ions in solution, and the
measurement of dissolved lead in toxicity tests
is essential for a realistic result. Organic compounds
of lead are more toxic to fish than inorganic lead
salts (WHO 1995).
Sediment dwelling organisms
Lead accumulates in sediments and can pose a hazard
to sediment-dwelling organisms at concentrations
above 30.2 mg kg-1, according to Canadian
interim marine sediment quality guidelines.
Bioaccumulation
In aquatic ecosystems, uptake by primary producers
and consumers seems to be determined by the bioavailability
of the lead. The uptake and accumulation of lead
by aquatic organisms from water and sediment are
influenced by various environmental factors, such
as temperature, salinity, and pH, as well as humic
and alginic acid content.
In many organisms, it is unclear whether lead is
adsorbed onto the organism or actually taken up.
Consumers take up lead from their contaminated food,
often to high concentrations, but without biomagnification
(WHO 1995).
Lead uptake by fish reaches equilibrium only after
a number of weeks of exposure. Lead is accumulated
mostly in gill, liver, kidney, and bone. Fish eggs
show increasing lead levels with increased exposure
concentration, and there are indications that lead
is present on the egg surface but not accumulated
in the embryo. In contrast to inorganic lead compounds,
tetraalkyllead is rapidly taken up by fish and rapidly
eliminated after the end of the exposure (WHO 1995).
Alkyllead was identified as the cause of a major
bird kill in the Mersey estuary in 1979/80 (NRA
1995). Approximately 2,500 birds from 20 species
were killed and alkyl lead was found in analyses
of bird tissue and in a common bivalve Macoma
balthica. The source of the pollution was traced
to an industrial discharge from a manufacturer of
tetraalkyllead.
In shellfish, lead concentrations are higher in
the calcium-rich shell than in the soft tissue;
they relate to the concentrations in sediment. Lead
concentrations in some marine fish are higher in
gills and skin than in other tissues, but this may
be largely due to adsorption. Liver levels increase
significantly with age (WHO 1995).
In dolphins, lead is transferred from mothers to
offspring during fetal development and lactation.
This might be related to the calcium metabolism.
In studies on the common porpoise Phocoena phocoena
from the east coast of Scotland, Falconer et
al (1983) found that lead residues were below
detectable limits (0.5 mg kg-1). The
sampled animals had died after becoming entangled
in cod nets. The tissues analysed were the brain,
liver, kidney, heart, and spleen. Honda et al
(1986) sampled striped dolphin Stenella coeruleoalba
and found significant accumulation of lead in the
bone of offspring during the suckling period. Significantly
more lead was found in adult males than females.
The authors suggested that lead was removed from
the mother via the milk and as the result of parturition.
Lead levels ranged between 0.09 and 0.74 mg kg-1
wet weight.
Potential effects on interest
features of European marine sites
The potential effects include:
- acute toxicity to algae, invertebrates and fish
at concentrations of dissolved lead above the
proposed EQS of 10 µg l-1
(annual average) in the water column. A lower
guideline value of 0.5µg l-1
of dissolved lead has been suggested by Grimwood
and Dixon (1997) for sites of nature conservation
importance where particularly sensitive algal
species are to be protected;
- accumulation in sediments and can pose a hazard
to sediment-dwelling organisms at concentrations
above 30.2 mg kg-1, according to Canadian
interim marine sediment quality guidelines;
- bioaccumulation in the food chain posing a hazard
to fish, birds and Annex II sea mammals.
Next Section
References
|