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residues in Risso’s dolphins (Grampus griseus) from the Mediter-
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total mercury, methylmercury and selenium in muscle tissues and in
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0025-326X/02/$ - see front matter Ó 2002 Published by Elsevier Science Ltd.
PII: S 0 0 2 5 - 3 2 6 X ( 0 1 ) 0 0 2 2 1 - 1
Chlorinated pesticides in mussels from Guanabara Bay,
Rio de Janeiro, Brazil
uning, I. Moreira *
A.P. Xavier de Brito, I.M.R. De Andrade Br€
Department of Chemistry, Pontifıcia Universidade Cat
olica, Rua Marqu^
Chlorinated pesticides are common pollutants in
coastal areas and estuaries (Farrington, 1983; Tanabe
et al., 1989; Sanchez et al., 1993; Ruangwises et al.,
1994; Jernelov, 1996), resulting mainly from agricultural
practices and insect control. As hydrophobic com-
pounds, organochlorines exhibit a high affinity for lipids
and tend to accumulate in marine organisms. Mussels
have traditionally been used as sentinels for monitoring
such compounds.
Guanabara Bay is a coastal area of great economic
importance in the Brazilian south eastern coast line. It is
surrounded by three cities (Rio de Janeiro, S~ao Goncßalo
and Niteroi) with a total population of about 11 million.
The Bay receives discharges of chemical contami-
nants together with domestic, industrial and agricultural
wastewaters. Guanabara Bay is 384 km2 in area, and
the climate involves warm, wet summers and dry, cool
winters. A detailed study of the Bay has been published
by Kjerfve et al. (1997). Its average water depth is 5.7 m,
although the central channel reaches 30 m in depth. The
rate of sediment deposition is 1:6  0:6 cm yr 1 (Godoy
et al., 1998). The mean freshwater discharge is 100 
59 m3 s 1 and is highest in the summer.
The present paper reports the occurrence of eight
chlorinated pesticides in common mussels Perna perna
sampled at five stations within the Bay. In Brazil, the use
of these compounds has been banned or restricted. Only
* Corresponding author.
79
Storelli, M.M., Zizzo, N., Marcotrigiano, G.O., 1999. Heavy metals
and methylmercury in tissues of Risso’s dolphin (Grampus griseus)
and Cuvier’s beaked whale (Ziphius cavirostris) stranded in Italy
(South Adriatic Sea). Bulletin of Environmental Contamination
and Toxicology 63, 703–710.
Wagemann, R., Hunt, R., Klaverkamp, J.F., 1984. Subcellular distri-
bution of heavy metals in liver and kidney of a narwhal whale
(Monodon monoceros): an evaluation for the presence of metallo-
thionein. Comparative Biochemistry and Physiology 78C, 301–
307.
Yagle, M.K., Palmiter, R.D., 1985. Coordinate regulation of mouse
metallothionein I and II genes by heavy metals and glucocorticoids.
Molecular and Cellular Biology 5, 291–294.
es de S~
ao Vicente, 225, CEP. 22453-900, Rio de Janeiro, Brazil
public health institutions have permission to use DDT
against specific pests causing serious illnesses, e.g.
dengue fever or Chagas’ disease. A trend away from the
use of organochlorines exists, with organophosphate use
becoming more common.
Fig. 1 presents a map of Guanabara Bay and the
collection sites. Perna perna can be found at several lo-
cations near the entrance of the Bay, where the mussels
either grow naturally or are cultivated by fishermen.
Station 1 was located at the mussel cultivation area of
the Jurujuba Fishermen Corporation; Station 2, near the
Santos-Dumont City Airport; Stations 3 and 4 on pillars
of the Rio de Janeiro-Niter oi bridge; and Station 5 lies
in Niteroi, on the Boa Viagem Beach.
The samples were collected during the first two weeks
of August (winter) and in December (summer) 1996.
The mussels were wrapped in aluminum foil previously
rinsed with a series of pesticide grade solvents (acetone,
ethanol and normal hexane), and were kept frozen until
reaching the laboratory. 10 mussels of similar size (4–6
cm) were composited for each location. The soft tissues
were separated from the valves and were freeze-dried,
prior to grinding and homogenising.
The samples (2 g) were spiked with 20 ll of n-hexane
containing 0:53 lg ml 1 of tetrachlorometaxylene
(TCMX) which was used as an internal standard. The
samples were then Soxhlet extracted for 24 h with 200 ml
of pesticide-grade hexane purified through Florisil col-
umns.
The extract was concentrated to about 10 ml in a
rotary evaporator and cleaned up by vigorous shaking
80 Baseline / Marine Pollution Bulletin 44 (2002) 71–81

analytical standard. TCB was also used to determine the

Fig. 1. A map of Guanabara Bay, showing the sampling stations.
with 2 ml of concentrated sulphuric acid. Phase sepa-
ration was achieved after 12 h in an icebox; the upper
hexane layer was removed and passed through an alu-
mina column deactivated with 5% water. The solution
was eluted with a mixture of hexane-dichloromethane
(90:10) and evaporated under nitrogen. The concen-
trated extract was transferred to previously weighed
glass ampoules. The sample was weighed and an aliquot
of 0.5 ml was transferred into an auto sampler vial
where trichlorobenzene (TCB) was added as an internal
relative electron-capture detector response factors of the
eight organochlorinated pesticide standards.
The extracts were analysed in a gas chromatograph
(Varian Star 3600 CV Model) using Ni63 electron-cap-
ture detection and a fused silica DB-5 capillary column
of 50 m  0:25 mm and film thickness 0:25 lm. Splitless
mode injections of 1 ll volume were used for all samples.
The column temperature was programmed from 80 °C
to 205 °C at 5 °C min 1 , with an isothermal period of 15
min, followed by a second programme from 205 °C
to 290 °C at 2 °C min 1 . The analytical conditions were
chosen to assure complete separation of the pesticides of
interest from PCB peaks present in the samples.
The extraction procedure was applied to a certified
standard (Marine Environmental Laboratory, Monaco)
for pesticide mussel contamination. The results obtained
for the certified sample were within the quoted confi-
dence intervals. The extraction recoveries were calcu-
lated for the samples with added TCMX, and offered a
mean value of 76%.
Table 1 shows the contamination of the mussels of
Guanabara Bay. All monitored pesticides were detected
at each station, and in general their concentrations were
higher during the dry season (August). This is probably
caused by the higher dilution of inflowing pesticide
residues in the rainy summer season (in December).
In general, the concentrations of the DDT group of
pesticides were higher than those of the other orga-
nochlorines measured here. Amongst these, DDE pre-
dominated in most samples, although the proportion of
unmetabolised DDT was significant in almost all sam-
ples, at both times of sampling. It is clear that DDT
continues to be washed into the estuary from sources
within the catchment.
The concentrations of aldrin, dieldrin and lindane
were all similar in general terms, and varied little be-
tween most of the sites/times of sampling. By compari-
son, the levels of HCB found in P. perna were mostly
low.
The spatial differences between the sites were not
particularly marked, and were inconsistent. However,

Table 1
1
Concentrations of organochlorine pesticides (ng g dry weight) in mussels from Guanabara Bay, Brazil
August December
Station 1 2 3 4 5 1 2 3 5
HCB 0.16 4.59 0.15 0.07 0.64 0.001 0.0002 1.66 0.90
Lindane 3.23 2.61 1.93 4.45 5.89 0.82 0.81 0.89 1.02
DDE 18.3 5.20 43.9 0.60 13.6 4.91 3.53 9.89 21.7
DDD 2.05 1.31 6.53 2.40 19.5 0.63 0.91 0.28 5.80
DDT 16.9 6.86 13.6 6.55 5.53 3.30 2.40 0.34 4.19
Aldrin 2.26 3.42 1.76 3.83 7.29 0.57 1.34 0.63 1.07
Dieldrin 2.67 2.87 14.9 4.01 5.08 2.66 1.50 2.47 0.54
    
Endrin 9.91 12.3 2.35 1.49
No sample could be taken at location No. 4 in December 1996.
*
Not determined, due to interference of peaks.
 Baseline / Marine Pollution Bulletin 44 (2002) 71–81
there was a trend towards lower pesticide levels in the
mussels from Station 2, near the entrance to the Bay.
Acknowledgements
This work was sponsored by CAPES. A.P. Xavier de
Brito and I.M.R. de Andrade Br€uning are thankful re-
spectively to CNPq and FAPERJ for financial support.
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