Benzene
Entry into the marine environment
Benzene (C6H6) is a liquid
at room temperature and pressure, is soluble in
water (720-2,200 mg l-1 variously
reported, with probable typical values in freshwater
of 720 mg l-1 and in seawater
of 1,224-1,550 mg l-1), has a low
to moderate log Kow value (2.13) and is highly volatile.
Production of benzene is associated primarily (>90%)
with the petrochemical industry, with a smaller
proportion produced as a by-product of coke production
and small quantities derived from natural gas. Benzene
is produced widely in the EC at high tonnage, including
in the UK. Annual UK production was variously estimated
around 690-1,025 Ktonnes during 1988-1990, with
estimated annual capacity around 1,210 Ktonnes (Nielsen
et al 1991) to 1,405 Ktonnes, at six sites
(ChemInform 1992). The UK is a net exporter, with
estimated usage in 1988-1990 of 694-879 Ktonnes
(Nielsen et al 1991).
Most benzene is used as a constituent of BTX (benzene-toluene-xylene)
in vehicle, aviation and other fuels, where benzene
is used to increase the octane rating. This use
has increased globally with the widespread introduction
of unleaded petrol and the increasing use of vehicular
transport in developing nations. However, in the
EC and elsewhere, the benzene content of fuels is
now coming under closer scrutiny and control. Benzene
is limited to 2% by volume in leaded and unleaded
fuel in the UK (i.e. below the 5% permitted by EU
legislation). The other major area of use is as
an intermediate in chemicals manufacture, particularly
in the production of styrene, cyclohexane, ethylbenzene,
nitrobenzenes and cumene. Benzene has also had widespread
use as a solvent, although this is now declining
and is probably insignificant in the UK; it is no
longer regarded as a commercial solvent by the UK
Hydrocarbon Solvent Association (Hedgecott and Lewis
1997).
During production and use, benzene is released
primarily to the atmosphere, although it is quite
mobile between environmental compartments. The
principal anthropogenic releases of benzene include:
- accidental and deliberate release of crude oils
and petrochemical products (including during refining
of crude oils and distribution and use of products);
- production of benzene and derivative chemicals;
exhaust emissions from fossil fuel combustion;
and
- emissions from coal tar distillation plants
and coal processing plants.
Entry into water may be direct or via atmospheric
deposition, run-off and leaching. Low but significant
levels may also arise from releases from natural
sources, such as vegetation and fossil fuels.
Recorded levels in the environment
Benzene has been reported in oceans, estuaries,
precipitation, rivers, groundwaters, potable sources
and drinking water, as well as aquatic sediments
and biota (Jones et al 1990, Nielsen et
al 1991). High usage and release, high
mobility in the atmosphere, and natural sources
all contribute to widespread occurrence in waters.
Many of the data are for estuarine and coastal
waters, with benzene apparently detected in relation
to both industrial discharges and releases during
oil extraction and transport. However, Hedgecott
and Lewis (1997) concluded that none of the reported
average concentrations in surface waters exceeded
the proposed annual average EQSs of 30 µg l-1
benzene in fresh and salt waters.
In the North-East region of the Environment Agency,
23% of 823 river and estuary samples over the period
1993-95 contained benzene, with a mean concentration
of under 2 µg l-1 and
highest concentrations of 312 and 54 µg l-1
(the only values that were higher than the proposed
EQSs). Only one of 26 seawater samples contained
detectable benzene (Hedgecott and Lewis 1997).
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. However, benzene was not monitored in
either survey.
The available data suggest that, while benzene
has been detected in UK coastal and estuarine waters,
in general, concentrations do not exceed relevant
quality standards derived for the protection of
saltwater life.
Fate and behaviour in the marine
environment
Hedgecott and Lewis (1997) reviewed data on the
fate and behaviour of benzene. Benzene appears to
be susceptible to microbial degradation by a variety
of species. Mixed aerobic cultures have been
reported to degrade benzene, with half-lives as
low as 15-20 hours up to a few days or more
depending on the source of the inoculum and the
history of pre-exposure. Degradation in pure aerobic
cultures of a variety of bacterial species has also
been reported, with Pseudomonas spp. apparently
being the major environmental degraders. Anaerobic
degradation can potentially occur but is apparently
subject to a long lag period (of the order of 20
weeks) and is nitrogen-limited. Without additional
nitrogen, degradation has been reported to take
six months to three years.
Only a low to moderate tendency to sorb to organic
solids is suggested by the log Kow value of 2.13
and log Koc value of 1.91. In surface waters, only
small amounts of benzene will sorb to aquatic sediments
(Hedgecott and Lewis 1997).
Benzene is very volatile and is probably the major
single removal process in most surface waters, particularly
under conditions unfavourable to biodegradation.
Theoretical volatilisation half-lives of 37 and
290 minutes have been calculated for a 1 m
deep water column with completely mixed water and
still water respectively. The importance of mixing
in increasing the rate of volatilisation has also
been demonstrated in experimental mesocosms, with
half-lives of 13 days in winter (well mixed) but
23 days in spring (less well mixed) (Hedgecott and
Lewis 1997).
Effects on the marine environment
Toxicity to marine organisms
An exhaustive literature review on the toxicity
of benzene 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 (Hedgecott and Lewis 1997). The
most sensitive groups of organisms have been identified.
Hedgecott and Lewis (1997) reviewed data on the
aquatic toxicity of benzene. In a previous review
(Jones et al 1990), the authors found that
saltwater data were primarily derived from tests
using static exposure conditions and nominal exposure
concentrations, and there were some concerns that
these would under-estimate benzene=s toxicity. Most of the information was derived
from acute studies, and the lowest reliable data
were acute LC50s of 4.9 mg l-1 for sockeye
salmon O. nerka and 5.5 mg l-1
for Dolly Varden char Salvelinus malma. These
results were based on analysed benzene exposures
and were, therefore, considered to be reliable.
However, Jones et al (1990) recommended that
further research with echinoderms (which were found
to be potentially sensitive) should be undertaken.
Additional data for bacteria (one species), invertebrates
(five species) and fish (two species) were summarised
by Hedgecott and Lewis (1997). All from acute studies,
apart from one chronic study with an edible crab
Scylla serrata . This appeared to
be the most sensitive organism under acute exposure,
with 72 hour LC50s of 3.3 and 4.6 mg l-1,
depending on reproductive status. In the
chronic study, biochemical changes were seen when
exposed for 3-30 days to 0.56 mg l-1
or higher. However, their reliability was uncertain
(Hedgecott and Lewis 1997). The lowest toxicity
data based on analysis of benzene are a 96 hour
LC50 of 9.03 mg l-1 for the sole
Solea solea. No data for sediment dwelling
organisms could be located.
Bioaccumulation
Data summarised in Jones et al (1990) for
freshwater and saltwater studies were limited, but
indicated that bioaccumulation of benzene was not
significant, with maximum BCF values of 225 in fresh
waters and 135 for salt waters. Few additional
bioaccumulation data were available for Hedgecott
and Lewis (1997), but they do not indicate higher
bioaccumulation potential than that indicated previously.
Potential effects on the interest
features of European marine sites
Potential effects includes:
- Toxicity of benzene to invertebrates and fish
at concentrations above the EQS of 30 µg
l-1 (annual average) in the water column.
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References
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