Organotins
Entry into the marine environment
The principal organotins of concern are compounds
of tributyltin (TBT). However, triphenyltins have
also been used in antifoulant paints.
Tributyltin oxide (TBTO) is the commercially available
active ingredient. TBTO is poorly soluble in water,
varying between <1 and >100 mg l-1,
depending on the pH, temperature and anions present
in the water. In seawater and under normal conditions,
TBT exists as three species (hydroxide, chloride
and carbonate) which remain in equilibrium. The
log Kow is 3.54 for seawater indicating that it
partitions to the organic solvent and adsorbs strongly
to particulate matter (WHO 1990).
TBT compounds have been registered as molluscicides,
antifoulants (on boats, ships, quays, buoys, crab
pots, fish nets and cages), wood preservatives (see
Section B33), slimicides on masonry, disinfectants,
and as biocides for cooling systems, power station
cooling towers, pulp and paper mills, breweries,
leather processing and textile mills (WHO 1990).
There are four main ways in which TBTs can enter
the marine environment:
- during the application of the antifouling paint
to boats or cage fish farm nets;
- leaching from paint on the hulls of vessels
or from cage fish farm nets;
- when paint is removed;
- when paint remnants are discarded.
Controls on the use of TBT in antifouling paints
were introduced in 1986 when the sale of TBT-based
paints was banned. In 1987, the use of TBT-based
paints on boats under 25 m and mariculture equipment
was also prohibited. Further controls are proposed.
These measures have reduced the potential routes
of entry into the marine environment and successfully
reduced environmental concentrations (Waite et
al 1991). However, because TBT is strongly adsorbed
to organic matter, the sediments retain concentrations
of TBT which can be mobilised when the sediment
is disturbed.
Recorded levels in the marine
environment
TBT is found in the water column, sediments and
the biota. Higher levels have been reported close
to pleasure boating activity, especially in or near
marinas, boat yards and dry docks (WHO 1990). In
Scotland, high levels have been reported in sea
lochs where cage fish farming occurs. WHO (1990)
and Waite et al (1991) reported concentrations
in the water column, sediment and biota but these
were for measurements taken in the late 1980s and
WHO (1990) indicated that 'older' measurements may not be comparable with
>newer=
measurements because of advances in analytical techniques.
Michel and Averty (1999) report concentrations
of TBT in the water column at marinas and commercial
and military harbours on the French coast of the
English channel in 1997 ranging from 0.0017 to 0.0877
mg l-1
and 0.0023 to 0.280 mg
l-1 respectively. The majority of these
measurements are above the EQS in the UK (0.002
mg l-1).
Recent monitoring of TBT in the marine environment
has been undertaken by using biological effects
monitoring. Gibbs et al (1987) conclusively
linked the condition of imposex in gastropod molluscs
to the presence of organotins in the environment.
This phenomenon was first observed in dogwhelks.
The measurement of the degree of imposex in this
species has developed into an effective monitoring
technique for organotins which is cheaper and more
sensitive than measuring chemical determinands (MPMMG
1998). This technique was included in the National
Monitoring Programme and results were presented
from Northern Ireland for 1994 in MPMMG (1998).
Dogwhelks from sites within Belfast Lough showed
clear signs of the imposex phenomenon, indicating
the continuing presence of organotins. For the North
Sea coast of the UK, similar results were derived
from the TBT Imposex Survey of the North Sea (Harding
et al 1997 cited in MPMMG 1998). This survey
indicated that imposex remained widespread throughout
the North Sea and English Channel from Shetland
to Land's End. Harding et al (1998) report
results for Western Coastal areas (including the
UK west coast and coast of Northern Ireland and
the Irish Republic) sampled in 1997 and concluded
that the effects of TBT pollution could be observed
over most of the area. Only at sites very close
to sources of pollution (commercial and fishing
harbours) could severe imposex effects be observed
and at sites where TBT was once used (marinas and
cage fish farm locations) measures of imposex could
not be distinguished from background.
CEFAS (1998) report concentrations of monobutyltin
(MBT), dibutyltin (DBT) and TBT in the livers of
porpoises and grey seals found stranded around the
coast of England and Wales between 1992 and 1996.
Concentrations of total butyltins (the sum of MBT,
DBT and TBT) ranged from 22 to 640
mg kg-1 wet weight in porpoise
and 3 to 22 mg
kg-1 wet weight in grey seals. DBT was
the dominant form of organotin in the liver.
Fate and behaviour in the marine
environment
The main removal process for TBT in the water column
is through adsorption onto particles. WHO (1990)
suggested that between 10 and 95% of TBTO was estimated
to undergo particle adsorption.
Progressive disappearance of adsorbed TBT is due
to degradation. Biodegradation by micro-organisms
and metabolism by higher organisms are probably
the dominant processes. Biodegradation depends on
environmental conditions, such as temperature, oxygenation,
pH, level of mineral elements, the presence of easily
biodegradable organic substances for co-metabolism
and the nature of the microflora (WHO 1990). It
also depends on the TBT concentration being below
the lethal or inhibitory threshold of the micro-organisms.
TBT is broken down into DBT and MBT. Half-lives
for TBT in the environment vary widely (WHO 1990).
Effects on the marine environment
Toxicity to marine organisms
An exhaustive literature review on the toxicity
of organotins 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 (Zabel et al 1988, WHO 1990).
The most sensitive groups of organisms have been
identified.
TBT is very toxic to algae, molluscs, crustacea
and fish. TBT has been identified as an endocrine
disrupting substance (Environment Agency 1998) with
observable effects in gastropod molluscs and suggested
effects in marine mammals (CEFAS 1998).
The development of the motile spores of a green
macroalga was impaired by exposure to TBT (5-day
EC50 of 0.001 mg
l-1) and this stage was considered to
be the most sensitive. The growth of a marine angiosperm
was reduced at TBT concentrations of 1 mg kg-1
of sediment but no effect were observed at 0.1 mg
kg-1.
Marine molluscs have been observed to undergo a
number of changes in response to exposure to sub-lethal
concentrations of TBT, including shell deposition
of growing oyster, gonadal development and gender
of adult oysters, settlement, growth and mortality
of larval oysters and other bivalves and to cause
imposex in female gastropods (e.g. Smith 1981, Waldock
1986, Zabel et al 1988, WHO 1990). Credible
adverse effects have been observed in saltwaters
organisms in laboratory tests at concentrations
as low as 0.01mg l-1 (Zabel et al 1988).
The NOEL for spat of the most sensitive oyster species
Crassostrea gigas has been reported to be
in the region of 0.002 mg
l-1 (WHO 1990).
Imposex is a condition where the female gastropod
develops a penis and a vas deferens which in severe
cases block the genital pore causing reproductive
failure and premature death. WHO (1990) report a
NOEL for the development of imposex in female dogwhelks
of below 0.0015 mg l-1
of TBT. Imposex effects have been observed in whelks
Buccinum undatum and Neptunea antiqua
collected from the west coast of Scotland in 1997.
These effects were observed 10 years after the ban
on the use of TBT on small craft and cage fish farm
nets and the effects were attributed to TBT accumulated
in the sediment. No sediment concentrations of TBT
were measured and the degree of imposex was not
considered to be affecting the fishery potential
of these species (Poloczanska and Ansell 1999).
Copepods are the most sensitive group of crustaceans,
with 96-hour LC50s ranging from 0.6 to 2.2 mg
l-1 (WHO 1990). TBT reduces reproductive
performance, neonate survival and juvenile growth
in crustaceans.
The toxicity of TBT to marine fish is highly variable,
with 96-hour LC50s ranging from 1.5 to 36 mg
l-1 with larval stages more sensitive
than adults.
The EQS for TBT is 0.002 mg
l-1 in the water column.
Rees et al (1999) and Waldock et al
(1999) studied the epifaunal and infaunal benthic
communities respectively in the River Crouch, SE
England in relation to decreasing environmental
concentrations of TBT in water and sediment between
1986 and 1992. In both cases, changes in faunal
composition could not be conclusively linked to
decreasing TBT concentrations but faunal diversity
increased at sites in the upper estuary where TBT
levels were greater in 1987 and had been significantly
reduced by 1992.
More recent studies have been conducted to determine
the extent of organotin contamination in the tissues
of marine mammals. TBT is bioaccumulative and the
ability of cetaceans to metabolise TBT is considered
to be low (CEFAS 1998). Various studies have highlighted
butyltin accumulation in a range of cetacean species
from Japan and the north Pacific Ocean. Recent data
from CEFAS on the contamination of porpoises and
seals from around England and Wales have demonstrated
that low-level organotin contamination of marine
mammals occurs around the UK (CEFAS 1998). However,
CEFAS was unable to assess the significance of their
findings and stressed that further information was
needed on the threats facing these animals from
possible toxic and bioaccumulation effects.
Bioaccumulation
TBT bioaccumulates in organisms because of its
solubility in fat. WHO (1990) reported BCFs of up
to 7,000 in laboratory investigations with molluscs
and fish and higher values have been reported from
field studies. Uptake from food is more important
than uptake directly from the water.
Potential effects on the interest
features of European marine sites
Potential effects include:
- toxicity to algae, invertebrates (especially
molluscs) and fish of TBT in the water column
at concentrations above the EQS of 0.002 mg
l-1;
- toxicity to algae, invertebrates (especially
molluscs) and fish of triphenyltin and its derivatives
in the water column at concentrations above the
EQS of 0.008 mg l-1;
- the presence of TBT is monitored by the degree
of imposex in female gastropod molluscs rather
than by direct measurements of concentrations
of organotins in the water column or the sediments.
Where imposex is detected within a European marine
site, a precautionary approach should be adopted
in the control of TBT and activities associated
with its use (e.g. pleasure boating, cage fish
farming);
- accumulation of TBT in sediments which could
induce imposex in gastropod molluscs after several
years;
- bioaccumulation of TBT in the food chain posing
a potential hazard to birds and Annex II sea mammals;
- endocrine disruption impacts of TBT in invertebrates,
fish and potentially Annex II sea mammals.
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References
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