Chlorinated Ethanes
Entry into the marine environment
Chlorinated ethanes are used as industrial solvents
and in the production of other organochlorine compounds.
They are also used as dry-cleaning agents, as anaesthetics,
in the manufacture of plastics and textiles and
in the production of tetraethyllead and vinyl chloride
(CCME 1992). Chloroethanes are also formed in small
amounts by the aqueous chlorination of effluents.
Potential sources of contamination include direct
discharge of wastewaters, accidental spillages and
deposition from the atmosphere. Low level contamination
of surface water by rainwater was reported by McConnel
(1977) who measured the concentration of 1,1,1-TCA
in two UK upland reservoirs before and after a period
of prolonged rain in November 1974. The concentrations
of 1,1,1-TCA in the reservoirs increased from 13
to 21 ppb at one site and from 12 to 41 ppb at the
other. The levels occurring in rainwater are low
(generally less than 0.1 µg l-1)
and it is thought that contamination of surface
and groundwater is more likely to result from direct
discharge of solvents to water or accidental spills
to the ground, rather than by transfer of solvent
vapour from the air (Pearson and McConnel 1975).
Information summarised in Rees and Bowen (1992)
concluded that major global producers of 1,1,1-TCA
included the United States, Western Europe and Japan.
For 1983, global production of 1,1,1-TCA was estimated
to be 537 ktonne/year. Production of 1,1,2-TCA is
thought to be much lower, and was around 80 ktonne/year
in 1983 (ECETOC 1988). The consumption of 1,1,1-TCA
in Western Europe increased in the 1960s and 1970s
as 1,1,1-TCA replaced other more reactive chemical
compounds, but has remained fairly constant at around
150 ktonne/year since 1979 ( CEFIC 1986). UK consumption
was estimated to account for just over 20% of the
total European consumption at around 30 ktonne/year
in 1984 (CEFIC 1986).
Chlorinated ethanes are low-molecular weight saturated
compounds containing two carbon atoms in which one
or more hydrogen atoms have been substituted with
chlorine. With the exception of hexachlorethane,
all chloroethanes are low-boiling liquids, most
are relatively volatile and water-soluble. In general,
both volatility and water solubility decrease with
increasing chlorine substitution. Volatilisation
can be considered to be the primary removal process
from water (CCME 1992).
Rates of disappearance of around 90% within one
to two hours have been reported for both isomers
of TCA from slowly stirred water. Similar rates
were observed in the presence of natural absorbents,
such as limestone and peat (Dilling et al 1975).
Recorded levels in the marine
environment
In saltwater waters, Pearson (1982) estimated typical
levels to be around 0.01 µg l-1
in offshore areas and 0.15 µg l-1
for inshore areas. In Liverpool bay, in an area
receiving discharges from 1,1,1-TCA production,
levels were much higher at 0.2 to 3.3 µg l-1
(Pearson and McConnel 1975).
Monitoring data from the National Rivers Authority
and the National Monitoring Programme Survey of
the Quality of UK Coastal Waters are presented in
Appendix D. Monitoring data are available for trichloroethane,
but no water column concentrations were found to
exceed the EQS value (see Appendix D).
The available data suggest that concentrations
of trichloroethanes in UK coastal and estuarine
water are unlikely to exceed relevant quality standards
derived for the protection of saltwater life.
Pearson and McConnel (1975) determined the levels
of 1,1,1-TCA in a wide range of organisms chosen
to represent a wide range of trophic levels. Most
of the samples were taken from Liverpool Bay, an
area where the main UK organochlorine plants are
situated. However, other samples taken from the
Thames Estuary, the Firth of Forth and Tees Bay
also showed some degree of contamination. The levels
of 1,1,1-TCA (in µg/kg wet tissue) are:
Plankton 0.03-10.7;
Saltwater algae 10-25;
Molluscs 0.05-10;
Crustacea 0.7-34;
Fish flesh 0.7-5;
Fish liver 1-15;
Water birds eggs 3-30;
Water bird liver 1-4;
Seal liver 0.2-4;
Seal blubber 8-24.
Fate and behaviour in the marine
environment
Direct photolysis, oxidation and hydrolysis are
not expected to be significant removal processes
for chloroethanes in the aquatic environment. TCA
has been shown to undergo both chemical and biotic
degradation, but the long half-lives for the reactions
involving both isomers suggest that degradation
is not an important loss mechanism from surface
water. Little or no degradation of chloroethanes
was found during standard BOD (biochemical oxygen
demand) bottle test (Pearson and McConnel 1975).
As the lower chlorinated compounds have slight
affinities for lipophilic materials, sorption to
organic-rich material is considered to be minimal.
In laboratory tests, little or no sorption to inorganic
or organic material was observed (Dilling et
al 1975) .
Effects on the marine environment
Toxicity to marine organisms
An exhaustive literature review on the toxicity
of chlorinated ethanes 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 (Rees and Bowen 1992).
The most sensitive groups of organisms have been
identified.
Rees and Bowen (1992) reviewed data on the aquatic
toxicity of TCAs. The authors found few data on
the toxicity of 1,1,1-TCA to saltwater life and
none of the data were from chronic tests. More data
were available for 1,1,2-TCA but most are derived
from two studies; Pearson and McConnel (1975) report
an LC50 of 5 mg l-1 and Craig (1983)
cites an unknown response at 0.5 mg l-1
of 1,1,1-TCA for the green algae Phaeodactylum
tricornutum suggesting that the toxicity of
1,1,1-TCA to algae is around 300 times greater in
saltwater than freshwater. These results are very
low compared to values obtained from similar tests
with 1,1,2-TCA in which 96 hour EC50s for growth
of 60, 170 and 200 mg l-1 were measured
for Phaeodactylum tricornutum, Chlorella
pyrenoidosa and Chlorella ovalis respectively
(Adema and Vink 1981).
Annelids appear to be relatively insensitive to
1,1,2-TCA. Adema and Vink (1981) estimated a 96
hour LC50 of 190 mg l-1 for Ophyrotrocha
diadema. While for three crustacean species,
Artemia salina, Crangon crangon and
Temora longicornis, 96 hour LC50s of 43 to
52 mg l-1 for the adult stage were
found for 1,1,2-TCA. Three week tests on Artemia
larvae estimated an EC50 of 15 mg l-1
and a No Observable Effect Concentration (NOEC)
of 10 mg l-1 both for reproduction.
For 1,1,1-TCA, LC50 values of 7.5 mg l-1
for Elminius modestus and 31.2 mg l-1
for Mysidopsis bahia have been calculated
(Pearson and McConnel 1975; US EPA 1980).
Fish
Acute LC50s for 1,1,1-TCA in saltwater of 33, 60
and 71 mg l-1 have been reported
for Limanda limanda, Cyprinodon variegatus
and Lagodon rhomboides respectively (Pearson
and McConnel 1975; Heitmuller et al 1981;
Craig 1983). Heitmuller et al (1981) also
estimated a 96 hour NOEC of 3.5 mg l-1
for mortality of Cyprinodon variegatus. No
data were found on the chronic toxicity of 1,1,1-TCA.
Adema and Vink (1981) estimated a 7-day LC50 for
1,1,2-TCA of 43 mg l-1 for adult
Gobius minutus. A lower 7-day LC50 of 27
mg l-1 was determined for larval plaice
Pleuronectes platessa. Chronic data were
available only for the egg/larval stages of Pleuronectes
platessa. No effects were observed on the mortality,
growth or development over eight weeks at 3.0 mg
l-1 1,1,2-TCA, and an LC50 of 5.5 mg l-1
was calculated for the same period.
No data could be located for sediment-dwelling
organisms.
Bioaccumulation
The potential for bioaccumulation of C1 and C2
hydrocarbons in the field was assessed by Pearson
and McConnel (1975). The authors determined the
levels of 1,1,1-TCA in the tissues of a wide range
of organisms in samples taken from Liverpool Bay
(an area where the major organochlorine industries
are situated), the Thames Estuary, the Firth of
Forth and Tees Bay. They found little evidence to
suggest extensive bioaccumulation and transfer to
food chains.
With the exception of hexachloroethane, most chloroethanes
have low octanol/water partition coefficients. On
this basis, only a slight potential to bioaccumulate
can be expected.
Potential effects on interest
features of European marine sites
Potential effects include:
- toxicity of 1,1,1 trichloroethane to algae,
invertebrates and fish at concentrations above
the EQS of 100 Fg
l-1 (annual average) and 1,000 µg
l-1 (maximum allowable concentration)
in the water column;
- toxicity of 1,1,2 trochloroethane to algae,
invertebrates and fish at concentrations above
the EQS of 300 Fg
l-1 (annual average) and 3,000 µg
l-1 (maximum allowable concentration)
in the water column
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References
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