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Cadmium contamination of three bivalve species (oysters, cockles
and clams) in Nord Médoc salt marshes (Gironde estuary, France) :
Geochemical survey and metal bioaccumulation kinetics
M. Baudrimont, J. Schäfer\ V. Marie, R. Maury-Brachet, C. Bossy1, G. Durrieu,
A. Palvadeau, E. Maneux\ A. Boudou and G. Blanc1
Laboratoire d'Écophysiologie et Écotoxicologie des Systèmes Aquatiques, LEESA,
Université de Bordeaux I, UMR 5805 du CNRS, EPOC, place du Dr. Peyneau, 33120 Arcachon,
France
1 Department of Geology and Oceanography, DGO, Université de Bordeaux I,
UMR 5805 du CNRS, EPOC, avenue des Facultés, 33405 Talence cedex, France
Abstract : A historical Cd pollution of the Lot-Garonne River system (France) bas led to the contamination of
sediment and water of the Gironde Estuary. In spite of the decrease of fluvial Cd inputs since the early 90ies, Cd
concentrations in the Gironde oysters remain higher than European norms (5 pg. g-1 dry mass) and the " zone D "
classification of the estuary prohibits bivalve production and harvesting for human consumption. A geochemical
survey in salt marshes used for aquaculture (crustaceans) has been conducted in order to assess the heavy métal
contamination level in these systems periodically alimented by the Gironde water, accompanied by caging
experiments on three bivalve species of economical interest : oysters (Crassostrea gigas), cockles (Cerastoderma
edule) and clams (Ruditapes philippinarum) to study heavy metal accumulation in these organisms. Distribution of
heavy metals in this system is controlled by biogeochemical processes and is independent of routine water
management. Contamination levels in the studied species indicate the high accumulation of Cd by oysters. On the
other hand, Cd concentrations in benthic species, such as cockles and clams, are clearly lower than European safety
limits for human consumption.
1. INTRODUCTION
A historical Cd pollution of the Lot and Garonne Rivers (south west France), originated from discharge in
the industrial basin of Decazeville, has led to the contamination of sediment and water of the Gironde
Estuary resulting in high Cd accumulation in oysters (Crassostrea gigas) [1]. Thus, the Gironde has been
classifie " zone D " (French law, Arrêté du 21/07/1995) and consequently bivalve production and
harvesting in the estuary for human consumption is prohibited.
In spite of the decrease of fluvial Cd inputs since the early 90ies [1], Cd concentrations in the
Gironde oysters remain higher than European norms, especially since. April 2002, when new, lower safety
limits were established (5 ig. g-1 dry mass ; CE N'466/2001, [2]). The interdiction of bivalves production
in the Gironde estuary restricts the aquaculture in the Nord Médoc sait marshes to kuruma prawn
(Penaeus japonicus) production. However, the presence of an important natural population of cockles
(Cerastoderma edule) in these systems has led the local professional association (CURUMA) to conduct
an interdisciplinary study coupling geochemical and ecotoxicological assessment, in order to enhance the
economical potential of the Nord Médoc sait marshes by benthic bivlaves production. This survey has
been conducted during 15 months in order to quantify the heavy metal contamination in three different
sait marshes, in condition of prawn production or without any crustaceans in the basins, along witb a
study on metal bioaccumulation in three bivalve species of economical interest : oysters (Crassostrea
gigas), cockles (Cerastoderma edule) and clams (Ruditapes philippinarum). Bivalves are known to
1 iC
accumulate large quantities of metals by their ventilation activity for nutritional and respiratory purposes,
and couid in this way indicate thé présence ofbioavaiiabte metats in thé basins. Data base analyses were
expected to aïlow the determination of pathways, dynamics and levels of contamination, especially of Cd.
The presented results were obtained in the " Bleu Médoc " basin, where prawn production was suspended,
but water management was continued.
2. STUDY AREA, MATERIALS and METHODS
2. 1 Study area
The Nord Médoc sait marshes (south west France, Fig. 1) are located near the mouth of the Gironde
estuary which is one of the major European estuaries (riverine water discharge : 34 x 109 rn3. yeaf', [1]).
These salt marshes, formerly constructed for salt production, are now used for aquaculture and kuruma
prawn (Panaeus japonicus) production. Typical basin sizes are 300x60 m with depths between 0. 7 to
1.
2 m. Brackish water supply for the breeding basins is realized by controlled input of estuarine water at
high tide, transporting nutrients but as polluants into the basins.
Gironde Estuary
Nord Médoc
salt niarshes 1
zizi
alo'rkau Dordogne river
aronne River
LoiRîverDecazevilleRiou-,Vort 50 km
River
Figure 1. Map of the Gironde Estuary and the Nord Médoc salt marshes (France).
2. 2 Geochemical survey
The geochemical characterization of the breeding basins is based on a 15 months observation of two types
of geochemical parameters :
Physico-chemical parameters (T°, salinity, dissolved oxygen concentrations and pH) were measured
every hour using automatic multiparameter probes (Hydrolab), which were installed at-30 cm above the
sediment surface. These measurements were completed by manual measurements at the water surface 2-4
times per week. Probes were checked, cleaned and calibrated each month, when stored data were
recovered. Particulate heavy metal concentrations in the sediment, in suspended particles (recovered by
pumping/centrifugation [3] and collected by sediment traps) and dissolved concentrations in the water
column were analysed by ICP-MS. Matrix separation for estuarine water analysis was done by
liquid solid extraction [3]. The applied analytical methods were continuously quality checked by analysis
of international certified reference materials (PACS-1, CRM-320, SLRS-3, SLRS-4, SLEW-2). Accuracy
was within 10% and precision was within 5 % for concentrations 10 times higher than detection limits.
2. 3. Ecotoxicological studies
Jointly to the geochemical survey, three bivalve species were transplante in the basins during 10 months
(from May 2000 to March 2001), either suspended in the water column for oysters (Crassostrea gigas) in
bags, or at the water/sediment interface for cockles (Cerastoderma edule) and clams (Ruditapes
philippinarum) in cages. Oysters were juveniles (8 mm of shell length) and originated from the Ile de Ré
(France), cockles and clams were one-year old, and were respectively indigeneous and imported from
Italy. Every 40 days, individuals were collected from each cage or bag. 5 sub-amples were used for
analysis of growth (size of the shell and total dry mass of the soft body-60°C during 48h) and heavy
metal concentrations after digestion step (3 hours in high purity nitric acid at 95°C) by Atomic
Absorption Spectrophotometry (AAS Varian 400). Validity of the analytical method was checked
periodically using biological standard relerence material (TORT-2, DORM-2-CNRC, Ottawa, ON,
Canada).
3. RESULTS and CONCLUSIONS
The evolution of the physico-chemical parameters as temperature dissolved 02 and pH show distinct daily
variations reflecting photosynthesis and respiration, whereas salinity varies with basin alimentation,
evaporation and precipitation (Fig. 2). In summer, high water temperatures and intense biomass
production and degradation result in very low dissolved 02 concentrations, reaching minimum values of
<40 % of 02-saturation at 30 cm above the sediment in the early morning before sunrise. Vertical 02
profiles show that hypoxia increases with depth, causing anoxie conditions ( 1% 02-saur. ; data not
shown) at the sediment surface.
r 9 Although in the breeding basins high and very
-'- ! 30 8 6 variable Cd concentrations occurred in the
te ierature salinli'ty 8, 6
r'dissolved phase and in SPM recovered by the
6 6 20-v 8, 2 pumping/ centrifugation method [3], the particles
O pH, ^ collected in sediment traps and basin sediments
E : Si 7, 8 show low Cd concentrations similar to the local
fî 10- background (<0. 5 mg. kg-1). This suggests that
7, 4
trapped particles are similar to those in the upper
E 0 27 sediment layers. Current velocities were too low
7/257/30 8/4 8/9 8/148/198/248/29 913 9/8 (<0. 1 m. s-') to affect the geochemical
composition by grain size segregation.
Figure 2. Daily variations of T, pH, 02 and
salinity in the Therefore, the different concentrations in
breediiig basin. centrifuged aiid trapped particles are attributed to
dissolution processes in the redox gradient (early
0, 5 1 Cd sr'1 30 diagenesis). As the trapped material was sampled
0, 4 I 25 monthly, kinetics
_... Ï dissolution appear to be high, leading to the
rapid release of particulate metals into the water
R 0, 2 / ` " 15 i ; colurnn. Here, the metals can be adsorbed onto
0,
2 15
Q, >, 0 SPM or be stabilized within the dissolved phase
0'l....... 10 by complexation. As there is no apparent relation
00 1... 5 between dissolved Cd concentrations and salinity'514100 7/4/00 913/00 11/3/00 113/01 3/5/01 5/5/01 7/5/01 9/4/01 in the
breeding basins (Fig. 3), concentrations,
distribution and partition of heavy metals in this
Figure 3. Dissolved Cadmium concentrations in the system appears to be controlled mainly by
breeding basin
vs.
salinity biogeochemical processes and, to a lesser extent,
by water management.
Juveniles of oysters (Crassostrea gigas) showed a rapid and important increase of soft body dry weight
with respect to time, especially during spring and summer, characterized by important phytoplanctonic
algae supplies (Fig. 4). In winter, the weight of the oysters stabilized, in relation to the decrease of food
supplies and the change in climate conditions. Growth was then clearly correlated with abiotic factors
(temperature, dissolved 02 and pH) measured in the water column of the basin. For Cd concentrations, a
significant and quasi-linear increase was observed with time, reaching very high values at time T8 (March
2001), near 25, 000 ngCd/g (dw), corresponding to 5 times the authorized level for human consumption.
The comparison of Cd accumulation in the three species at time T5 (December 2000) showed
marked differences between contamination levels (Fig. 6), indicating the high impact of Cd on Oysters,
able to filter large quantities of water for respiratory and nutritional purposes. On the other hand, benthic
species, such as cockles (Cerastoderma edule) and clams (Ruditapes philippinarum), did not present
significant heavy metal contamination, always under the human consumption limit. These results are
consistent with low metal concentrations measured in thé basin sediment and in trapped particles, on the
contrary of ponctually high dissolved and particulate Cd levels in the water column.
0,5rtl:g'EType±1,96E-Typ.
a H. M'Err-Typ. 30000
t, . . Typ.-r-T
? " MMg< OtvMtt [° ! [J
3. ! 24000-r-r !
3 8 avetage ta avearge i 0
r 0, 4 i T ; 1 a 1
24000
0,3 18000
'B. s 11
0
z i
., P 0, 1 6000 1= = 1
. = !TO TI T2 T3 T4 TS T6 T7 T8 TO Tl T2 T3 T4 T5 T6 T7 T8
Sampling point Sampling point
Figure 4. Chair
mass
(a) and Cd accumulation levels (b) in the soft
parts
of Oysters. TO
to T8 are
the successive sampling
times of
one
caging experiment.
Cd (mg. kg'') Cd (mg. kg ")
0 1 2 3 0 1 2 3 24000 : . : Type----
5117100 1 average
2 [21/01 20000 0-5
$PM
-) ;..'______'j ?
2/21/01 SPM 0-5 16000
25-30 cn
9/26/00 X'B- ! 3
; Tr'ip !F'IZUUU
0-5
9126/00 15-20 Il February 2001
11/22/00
25-30 8000
2/21/01 5 pg/g (dw)
..............................................................................
0-5 4000
519/01 15-20
Cockles Clams Oysters
Figure 5.
Cd
contents
in SPM,
trap
sediments and Figure 6. Cadmium concentrations in the 3 studied bivalve
sediment. Dashed lines represent regional background species compared with European safety limits.
values and full lines polluted harbour sediments [5].
These results allowed CURUMA to obtain the safety classification of the Eau Médoc salt marshes
to
produce cockles and clams since January 2003, that enhances the economical potential of this region.
Acknowledgements
This work
was
funded by FEDER (PESCA),
« Conseil
Général de la Gironde
», « Agence
de l'Eau Adour-Garonne
M,
« District
de
la Pointe du Médoc
», «
Direction Régionale des Affaires Maritimes
» and by a Marie Curie fellowship (European
Community
program
" Energy, Environment and Sustainable Development "
; EVKI-CT-2000-5003. The study
was
supported
by GIS ECOBAG. The
project
was
conducted by the
"
Mission
de
valorisation-Breve » of University
Bordeaux 1. We thank
V. Roques-Duflo, H. Bouillard, Y. Lapaquellerie, N. Maillet and B. Etcheverria for technical support.
References
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[2j Schâfer, J. et Blanc. G. Sci. Tot. Environ., 298 (2002) 103-ilS.
[3] Kingston, H. M., Barnes, I. L., Brady, T. J. and Rains, T. C. Anal. Chem., 50 (1978) 2064-2070.
[4'l- Résudtats de la survei ! lance de la qualité du milieu marin littoral, IFREMER, RNO, 200 i.
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