Chromium
Entry into the marine environment
Chromium occurs ubiquitously in nature with natural
levels in uncontaminated waters ranging from fractions
of 1 µg to a few µg l-1.
Sea water contains less than 1 µg chromium
l-1 (US NAS, 1974), but the exact chemical
forms in which chromium is present in the ocean,
and surface water is unclear. Theoretically, chromium
can persist in the hexavalent state (Cr IV) in water
with a low organic matter content. In the trivalent
form (Cr III), chromium will form insoluble compounds
at the natural pH of water, unless protected by
complex formation. The exact distribution between
the trivalent and hexavalent state is unknown
Almost all the hexavalent chromium in the environment
arises from human activities. Chromium compounds
are used in ferrochrome production, electroplating,
pigment production, and tanning. These industries,
the burning of fossil fuels, and waste incineration
are sources of chromium in air and water. In the
hexavalent oxidation state, chromium is relatively
stable in air and pure water, but is reduced to
the trivalent state when it comes into contact with
organic matter in biota, soil, and water. There
is an environmental cycle for chromium, from rocks
and soils to water, biota, air, and back to the
soil. However, a substantial amount (estimated at
6.7 x 106 kg per year) is diverted from
this cycle by discharge into streams, and by run-off
and dumping into the sea. The ultimate repository
is ocean sediment (WHO 1988).
It appears that the zero-, di-, tri-, and hexavalent
oxidation states have biological importance. The
effects of the last two oxidation states are so
fundamentally different that they must always be
considered separately. The trivalent form is an
essential nutrient for Man, in amounts of 50 - 200
µg day-1 (WHO 1988) .
Recorded levels in the marine
environment
Concentrations of chromium have been measured in
water and sediments 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 have been summarised
in Appendix D. MPMMG (1998) should be consulted
for further details.
Grimwood and Dixon (1997) compiled available monitoring
data for chromium in water, sediments and biota
for marine sites of nature conservation importance
in England.
As an example of the recorded levels of dissolved
chromium in the marine environment, the following
concentrations have been reported by DETR (1998)
for some English estuaries (see tables below).
Fate and behaviour in the marine
environment
The solubility of trivalent chromium in sea water
varies with salinity and depends strongly on the
complexes actually present. The loss of Cr III from
solution by precipitation is unlikely to occur to
any great extent and the main removal process is
adsorption to suspended particles. Chromium in the
oxidised form (Cr IV) is very soluble and is not
adsorbed strongly to suspended particles in natural
waters (Mance et al 1984).
Minimum concentration (µg
l-1) of dissolved chromium in the water
column of some English estuaries (from DETR 1998)
|
1991
|
1992
|
1993
|
1994
|
1995
|
Tyne |
0.0
|
0.0
|
0.0
|
1.0
|
0.0
|
Wear |
6.0
|
0.0
|
0.0
|
1.1
|
0.0
|
Tees |
0.0
|
0.0
|
0.0
|
1.0
|
0.0
|
Ouse |
|
|
|
0.0
|
0.0
|
Wash |
|
|
|
0.0
|
0.0
|
Thames |
0.0
|
0.0
|
0.0
|
0.0
|
0.0
|
Tamar |
0.0
|
0.0
|
|
|
0.0
|
Average concentration (µg
l-1) of dissolved chromium in the water
column of some English estuaries (from DETR 1998)
|
1991
|
1992
|
1993
|
1994
|
1995
|
Tyne |
14.0
|
1.6
|
0.4
|
1.9
|
2.5
|
Wear |
17.7
|
0.7
|
0.6
|
8.2
|
0.8
|
Tees |
10.5
|
4.3
|
1.0
|
8.6
|
2.0
|
Ouse |
|
|
|
0.4
|
0.0
|
Wash |
|
|
|
0.0
|
0.0
|
Thames |
2.9
|
0.6
|
0.2
|
0.3
|
0.3
|
Tamar |
6.6
|
0.0
|
|
|
0.1
|
Maximum concentration (µg
l-1) of dissolved chromium in the water
column of some English estuaries (from DETR 1998)
|
1991
|
1992
|
1993
|
1994
|
1995
|
Tyne |
66.0
|
11.0
|
2.2
|
5.2
|
9.0
|
Wear |
44.0
|
4.0
|
1.6
|
19.0
|
3.0
|
Tees |
53.0
|
37.0
|
2.3
|
23.1
|
16.0
|
Ouse |
|
|
|
4.7
|
0.0
|
Wash |
|
|
|
0.0
|
0.0
|
Thames |
17.0
|
1.8
|
0.8
|
1.2
|
0.8
|
Tamar |
30.0
|
0.0
|
|
|
1.0
|
Effects on the marine environment
Toxicity to marine organisms
An exhaustive literature review on the toxicity
of chromium 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 (Mance et al 1984, Hunt
and Hedgecott 1992, Grimwood and Dixon 1997). The
most sensitive groups of organisms have been identified.
In 1984, Mance et al reviewed data on the
toxicity of chromium to saltwater organisms. The
authors found acute toxicity to be extremely variable.
Fish appeared to be considerably less sensitive
than invertebrates, although the data on fish larvae
indicated that these forms were particularly sensitive
to chromium contamination.
Mance et al (1984) proposed an EQS for the
protection of saltwater organisms of 15 µg
l-1, expressed as a dissolved annual
average concentration. (this is currently adopted
in UK legislation (HMSO 1989)). The EQS was established
by applying an arbitrary factor of 2 to the lowest
chronic effects (unspecified) concentration of 30
µg l-1 reported at that time
for the polychaete worm Neanthes arenaceodentata.
However, following a review of more recent toxicity
data by Hunt and Hedgecott (1992), a more stringent
EQS of 5 µg l-1 was proposed.
This value (also expressed a dissolved annual average)
is based on effect concentrations of 10 - 30 µg
l-1 reported for a range of organisms
tested in the laboratory and corresponds to the
application of a factor of 2 to the lower end of
this range.
A further review of data on the toxicity of chromium
to saltwater organisms (since the report by Hunt
and Hedgecott 1992) has been undertaken by Grimwood
and Dixon (1997). The authors found no reliable
toxicity data that indicated higher sensitivity
of saltwater organisms than that previously reported.
They recommended that the revised EQS of 5 µg
l-1 (dissolved annual average) was appropriate
for the protection of all saltwater life, although
where there is concern that the health of communities
in sites of nature conservation importance may be
compromised as a result of the presence of particularly
sensitive species, a lower value may be used as
a guideline. However, in the absence of any new
toxicity data, it was not possible to make any recommendations
for such a value.
Sediment-dwelling organisms
Chromium is found in sediments and can pose a hazard
to sediment dwelling organisms at concentrations
above 52.3 mg kg-1 according to Canadian
interim marine sediment quality guidelines.
Bioaccumulation
Hunt and Hedgecott (1992) reported some information
on the bioaccumulation of Cr IV. Laboratory experiments
on annelids, crustaceans and molluscs have resulted
in bioconcentration factors (BCFs) in the range
158 to 596 for annelids and 383 to 620 (based on
dry weights) for molluscs and crustaceans in the
laboratory. Much lower BCFs have been calculated
in the field: 0.46 to 15 for annelids and <1
for molluscs and crustaceans. These BCFs indicate
that chromium is not expected to bioaccumulate under
field conditions.
Potential effects on interest
features of European marine sites
Potential effects include:
- acute toxicity to invertebrates and fish at
concentrations of dissolved chromium above the
EQS of 5 µg l-1 (annual average)
in the water column;
- toxic effects to sediment dwelling-organisms
at concentrations above 52.3 mg kg-1
according to Canadian interim marine sediment
quality guidelines.
Next section
References
|