hydrocarbon contamination in mussels from guanabara bay
TRANSCRIPT
Hydrocarbon contamination in mussels from Guanabara Bay
Luıs A. Azevedo, Inai M.R. de Andrade Bruning, Isabel Moreira *
Department of Chemistry, Pontifıcia Universidade Catolica, Rua Marques de S.Vicente, 225, 22453-900 Gavea, Rio de Janeiro, Brazil
Guanabara Bay is the most important embayment on
the south eastern coast of Brazil. Three cities, Rio de Ja-
neiro, Niteroi and Sao Goncalo are located in the sur-
roundings with an estimated total population of 11million. Within the state of Rio de Janeiro, most of
the petroleum activities in Brazil are concentrated, and
around Guanabara Bay two refineries, several petro-
chemical plants, oil terminals, shipyards and offshore
platform maintenance installations render the bay prone
to hydrocarbon contamination.
Several studies have examined hydrocarbon contam-
ination in the waters (Hamacher, 1996; Hamacher et al.,2000) and sediments (Hamacher, 1996; Lima, 1996) of
Guanabara Bay. The present work searched for ali-
phatic and polyaromatic hydrocarbon (PAH) contami-
nation in mussels Perna perna, that grow near the
entrance of Guanabara Bay. Previously, such mussels
have been investigated for organochlorine accumulation
(Xavier de Brito et al., 2002).
Guanabara Bay is a typical tropical estuary withwarm, wet summers and dry, cool winters. A detailed
description of the Bay has been presented before
(Kjerfve et al., 1997; Godoy et al., 1998; Xavier de Brito
et al., 2002). Fig. 1 presents the map of Guanabara Bay
and the location of the five sampling stations. These sta-
tions were chosen in close vicinity to potential pollution
sources and in areas where mussel fishing or cultivation
is carried out for human consumption.Station 1 is located in the mussel cultivation area of
Jurujuba Fisherman Corporation; station 2, between
the Santos Dumont City Airport and the Marina da
Gloria, which is a public mussel collection place; station
3 is located around the second biggest pillar on the left
side of the Rio de Janeiro-Niteroi bridge; station 4 is
on the second biggest pillar of the right side of the same
bridge; and station 5 lies in Niteroi, on the Boa ViagemBeach, and is also a public mussel collection area. In the
innermost area of the bay, where mussels are seldom
found, no samples were collected. The mussels were
manually collected in August (winter) and in December
(summer), 1996. In December, no specimen was col-
lected in station 4, because suitably sized mussels for
monitoring could not be found, due to intense summer
fishing activity. The collected mussels were wrapped inaluminum foil and kept in iceboxes until reaching the
laboratory. They were then selected according to size
(4–6cm), with 10 individuals composing each sample.
The soft tissues were separated from the valves and were
freeze-dried. The material was ground and homogenizedand stored at �10 �C until extraction. The analytical
procedure used to detect the aromatic and aliphatic
contamination was that recommended by the National
Bureau of Standards (Wise et al., 1980).
Freeze-dried tissue (2g) was Sohxlet extracted for
20h using 200ml of methanol; saponification was car-
ried out by adding 50ml of KOH 0.5N aqueous solu-
tion, and the sample was then extracted for a further4h. The methanol extracts were shaken three times in
a separation funnel with 50ml of normal hexane. The
final hexane extracts were passed through an anhydrous
sodium sulphate column and finally concentrated in a
rotary evaporator to approximately 1ml. Octadecene-1
and 9,10 dihydroanthracene were added to the extracts
to evaluate the extraction recoveries for the aliphatic
and aromatic fractions, respectively. The hydrocarbonextracts were separated into aliphatic and aromatic
fractions in a silica:alumina (1:1) column, using 25ml
of n-hexane for eluting the aliphatic hydrocarbons,
25ml of hexane:dichloromethane mixture (4:1) and
25ml of hexane:dichloromethane (1:1) for recovering
the aromatics. On the top of the column, a thin layer
of anhydrous sodium sulphate was added in order to
eliminate eventual water residues. The separation be-tween the aliphatic and aromatic fractions was moni-
tored by UV spectrometry.
Both fractions were analyzed in a gas chromatograph
(Hewlett Packard 6890) equipped with a hydrogen flame
ionization detector and a fused silica DB-5 capillary col-
umn of 30m · 0.25mm dimensions and film thickness of
0.25lm. Splitless mode injections of 1ll volume were
used for all samples. Column temperature programmingstarted from 50 �C to 280 �C at a rate of 5 �Cmin�1, with
a final isothermal period of 15min. Helium and nitrogen
were carrier and make up gases at the flow rates of
1.0mlmin�1, and 44.0mlmin�1, respectively. Injector
and detector temperatures were 260 �C and 300 �C,respectively.
Quantitation was carried out by comparison with
internal standards, naphthalene and normal hexade-cane, respectively for aliphatic and aromatic fractions.
A certified mussel sample (IAEA 142) was analyzed
according to this procedure; the results were within the
confidence intervals for both aliphatic and polyaromatic
hydrocarbons. The average extraction recovery for the
* Corresponding author. Fax: +55 21 3114 1637.
E-mail address: [email protected] (I. Moreira).
1120 Baseline / Marine Pollution Bulletin 49 (2004) 1109–1126
aliphatic fractions was 92.8 ± 4.0%. For the aromatic
fractions, a mean value of 90.4 ± 2.9% was found.Fig. 2 shows the distribution of the total aliphatic
hydrocarbon concentrations for the collected samples
in winter and summer seasons. The concentrations
(C10–C32) were higher in August (winter) and ranged
from 520 to 1461ngg�1 dry weight, whereas in Decem-
ber (summer) the range was 309 to 829ngg�1 dry
weight. The most contaminated mussels were those col-
lected in winter in stations 3 and 4 located on the pillarsof the bridge. Those mussels filter water coming from
the inner area of the Bay, where refineries and petroleum
terminals are located.
The gas chromatographic profiles of the aliphatic
fraction from station 2 samples (both August and
December) exhibited higher concentration of naphth-
enic compounds in the C26 region, which is typical of
lube oils. The evaluation of the aliphatic fraction chro-matograms shows a similar pattern for each station for
both summer and winter seasons. This similarity leads
to the conclusion that the qualitative contamination
sources remain constant, although the higher concentra-
tions in the dry season are derived from the lower water
input to the Bay. When compared to other inhabited
coastal areas (Anderlini et al., 1981; Law and And-
rulewicz, 1983; Martin and Castle, 1984; Shaw et al.,1986) the aliphatic concentrations of Guanabara Bay
mussels are among the lowest.
Among the polyaromatic hydrocarbons, fluoranthene
was predominant at all stations, and its range was
approximately constant in winter and summer seasons
(41.5–128.9ngg�1 dry weight in August and 59.7–
123.5ngg�1 dry weight in December). Other coastal sys-
tems have reported this polyaromatic as the predomi-nant pollutant in mussels (Shaw et al., 1986;
Shchekaturina et al., 1995). Also for the aromatic frac-
tions, a similar distribution for both seasons in each
location was observed, indicating constant qualitative
exposure throughout the year. Total polyaromatic pol-
lution (Fig. 3), was also considerably higher in winter
(173–432ngg�1 dry weight) than in summer (68–
375ngg�1 dry weight). Again station 2 presented higherpolyaromatic concentrations for both seasons.
The higher polyaromatic hydrocarbon contamination
of station 2, located near the entrance channel of the
largest marina of the Bay, indicates that intense sport
and leisure boat traffic and maintenance contribute
significantly to PAH pollution in the Bay. Station 4,
however, presented the second highest concentration of
aliphatic and polyaromatic hydrocarbons, with achromatographic pattern of the aliphatic fraction typical
Fig. 1. Guanabara Bay with sampling collection sites.
Fig. 2. Total aliphatic hydrocarbon concentrations (ng/g dry weight).
Fig. 3. Total PAH concentrations (ng/g dry weight).
Baseline / Marine Pollution Bulletin 49 (2004) 1109–1126 1121
of petroleum origin, with marked UCM (unresolved
complex mixture) proving the industrial origin of the
contamination. The polyaromatic qualitative distribu-
tion is similar to those of other stations. In comparison
with other studies (Cocchieri et al., 1990; Shaw et al.,
1986; Shchekaturina et al., 1995) Guanabara Bay pre-sented mussel polyaromatic concentrations within the re-
ported ranges.
Acknowledgments
This work was sponsored by CAPES. Luis A. Azev-
edo and Inai M.R. de Andrade Bruning are thankfulrespectively to CNPq and FAPERJ for financial support.
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Intersex in Roe�s abalone (Haliotis roei) in Western Australia
Sara Sloan, Marthe Monique Gagnon *
Department of Environmental Biology, Curtin University of Technology, Perth 6845, Australia
Since the 1970s, tributyltin (TBT) has been used as
the active ingredient in antifouling paints applied tothe hulls of vessels to prevent the attachment and
growth of fouling organisms. The leaching of TBT in
marine waters has been associated with the induction
of imposex, the imposition of male characters onto a fe-
male organism. To date, imposex has been reported in
63 genera and 140 species worldwide (Terlizzi et al.,
2004; Reitsema et al., 2002). Even at extremely low con-
centrations such as 0.5ngL�1 imposex has been ob-
served in Nucella lapillus, a marine snail (Bryan et al.,
1987). The deleterious effects observed globally triggeredthe adoption of legislative restrictions regarding the
application of TBT in many countries. In 1991, the
Western Australian government implemented legislation
restricting the use of TBT to vessels greater than 25m in
length.
In 1998–1999, Reitsema et al. (2003) surveyed 16 sites
in the Perth metropolitan area, and found a significant
reduction in imposex symptoms in the whelk Thais
orbita at 11 sites relative to a 1991 survey. However,
sites close to commercial harbours and docks still main-
tained 100% imposexed females with 30% of these with
permanent sterility. Reitsema et al. (2003) also observed
* Corresponding author. Tel.: +61 8 92663723; fax: +61 8 92662495.
E-mail address: [email protected] (M.M. Gagnon).
1122 Baseline / Marine Pollution Bulletin 49 (2004) 1109–1126