Journal of Hazardous Materials 167 (2009) 953–958

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Cathodic protection by zinc sacrificial anodes: Impact on marine sediment

metallic contamination
C. Rousseau ∗ , F. Baraud, L. Leleyter, O. Gil
Equipe de Recherche en Physico-Chimie et Biotechnologies (ERPCB) EA3914, Université de Caen-Basse Normandie – Bd du Maréchal Juin – Bât. Sciences 2, 14000 Caen, France

a r t i c l e i n f o a b s t r a c t

Article history: Cathodic protection by sacrificial zinc anodes is often applied to prevent immerged metallic structures
Received 22 September 2008 from corrosion. But this technique induces the zinc anodes dissolution, which can induce marine sedi-
Received in revised form 21 January 2009 ments and seawater contamination. A large scale experiment, in natural seawater, was conducted during
Accepted 21 January 2009
12 months, in order to evaluate the potential environmental impact of this continuous zinc dissolution,
Available online 30 January 2009
and of some necessary cleaning operations of the anodes surfaces. The heavy metal (Cr, Cu, Pb and Zn)
concentration in water and sediment samples was monitored. A sequential extraction procedure was
Keywords:
applied on sediment samples to differentiate the zinc mobile fractions from the residual one. A signifi-
Sediment
Seawater
cant increase of zinc concentration was observed in water as well as in the surface sediments under the
Zinc specific operating conditions. Sediments then become a secondary pollution source, as the sorbed labile
Chemical extraction zinc can be remobilized to seawater.
Sacrificial anode © 2009 Elsevier B.V. All rights reserved.

1. Introduction
A successful way to prevent corrosion of metallic structures in
seawater is to apply cathodic protection. The technique consists in
lowering the structure electrical potential into its protection range,
which can be realised either by galvanic coupling with a sacrificial
anode (i.e., zinc or aluminium) or by the application of a fixed cur-
rent density with an inert anode. The cathodic currents induce the
reduction of dissolved oxygen (1), generating hydroxyl ions at the
very near polarized surface. This reaction then increases the inter-
facial pH and induces the precipitation of an inorganic layer, mainly
constituted of calcium carbonate and some magnesium compo-
nents (2 and 3). This mixed deposit is generally called “calcareous
deposit”. As this non-conductive deposit progressively covers the
surface, the overall rate of the cathodic reaction (oxygen reduction)
decreases. The anodes dissolution (i.e., zinc oxidation (4)) rate is
then lowered, when galvanic coupling is used to apply cathodic
protection.
O2 + 2H2 O + 4e− → 4OH−
Mg2+ + 2OH− → Mg(OH)2 (s)
Ca2+ + CO3 2− → CaCO3 (s)
Zn → Zn 2+
+ 2e −
∗ Corresponding author. Tel.: +33 2 31 56 74 91; fax: +33 2 31 56 73 03.
E-mail addresses: christelle.rousseau@unicaen.fr, rousseau christelle@hotmail.fr
(C. Rousseau).
Thus, the anode dissolution rate varies according to the cathodic
protection steps. At the very beginning, as the current demand
is the most important, the dissolution rate is the highest. Then,
when the calcareous deposit is forming and progressively cov-
ering the entire surface, the current demand decreases, which
then reduces the anode dissolution. Moreover, other phenomena
can occur at the anodes surfaces. For instance, suspended matter
can be deposited, or a layer of zinc oxides can be formed at the
anodes surfaces [1], isolating the sacrificial anode from the elec-
trolyte medium. Such phenomena reduce the cathodic protection
efficiency (as the potential then increases) but also consequently
reduce the anode oxidation and consequently, the zinc release.
Under controlled experimental conditions it might be necessary to
operate some cleaning of the anodes surfaces, in order to remove
these layers and to maintain an efficient cathodic potential. In har-
bours, these cleanings are naturally realised by the tide and the
current which tear out the scale. The zinc oxides, then liberated,
can be dissolved, which then induces an important input of zinc
into water.
(1)
The zinc sacrificial anodes are widely used to protect ships
(2) and harbour structures, which raises the question of local water
contamination by the solubilized zinc. In harbours, the increasing
(3) numbers of ships using zinc sacrificial anodes, combined to the
(4) lower renewal of the seawater by tide, contributes to an increase
of the water zinc level. Concentrations up to 25 ␮g L−1 , depend-
ing of the tide exposition, have been observed by Bird et al. [2],
whereas the zinc average concentrations in the open ocean are
inferior to 0.5 ␮g L−1 [3]. This input may cause ecological dam-
age, as zinc is recognized to be toxic up to 5 ␮g L−1 by the OSPAR

0304-3894/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2009.01.083
954 C. Rousseau et al. / Journal of Hazardous Materials 167 (2009) 953–958

Fig. 1. Scheme of the experimental tank (a) position of the immerged samples, (b) position of the buried samples

Convention ecotoxicological assessment criteria (EAC) [4]. More- 2. Experimental

over, zinc is bioaccumulable and can contaminate the food chain
[5].
Some of the solubilized zinc can be transferred to the sediment
phase, via sorption phenomena onto solid particles. In harbours,
zinc concentration in the sediment phase can be 2.5 times higher
than in non-contaminated areas [2].
As other heavy metals, the zinc toxicity depends on its total con-
centration but also on its mobility and reactivity with the ecosystem
constituents. Therefore, adsorbed metals onto solid particles are
potentially available as they may be dissolved due to changes in
the physicochemical properties of the environment, like salinity,
pH, redox conditions and/or organic chelators occurrence [6,7].
This potential mobilization (or lability) can be estimated by chem-
ical extraction procedures. Thus, sequential extraction procedure
(several steps) are used to differentiate mobile from residual frac-
tions, and to characterize the different labile fractions [6,8–10] as:
exchangeable fraction (weakly bound elements in equilibrium with
the dissolved phase), acido-soluble fraction (very sensitive to pH
variations), reducible or oxidable fractions (very sensitive to redox
conditions and microbiological activity). Sequential extractions are
then useful for solid speciation of particulate elements, to study
the origin, the fate, the biological and physicochemical availability
and transport of sorbed elements. According to several studies on
metal fractionation, zinc is one of the most mobile metals as mainly
associated with the non residual fraction sediments [11–16]. Gen-
erally, zinc is mainly associated to the acido-soluble and reducible
fractions [2,11,16,17]. Exchange reaction between the sediment and
water phase can then occurred as these labile fractions can lib-
erate elements under changing physicochemical conditions (pH,
redox potential variation), as during harbour dredging operations
for instance. Then, contaminated sediments can be considered as a
secondary pollution source towards water.
In order to evaluate the potential zinc contamination of sedi-
ments and seawater, due to the use of zinc sacrificial anodes, a large
scale experiment, with natural seawater, was conducted during 12
months. Cathodic protection was applied on carbon steel structures
2.1. Cathodic protection with zinc sacrificial anode
A large scale experiment was conducted, during 12 months, in a
tank (about 9 m3 ), supplied with decanted natural seawater, which
was pumped at 400 m from the shore (stable pH, equal to 8.1) at
the marine station of Luc-sur-Mer (Normandy, France). The water
temperature evolves with seasons from 14 ◦ C to 20 ◦ C. In the exper-
imental basin, a continuous seawater circulation is maintained at
5 m3 h−1 which allows a good oxygenation of the water, but let the
suspended matter settle down. An additional seawater inlet (freshly
pumped water), which represents 5% of the seawater rate, leads to
a total tank renewal each 4 h. A 70 L container, filled with natural
marine sediments (obtained from the seawater settling, particles
diameters <60 ␮m), is immersed in the tank. Some of the steel sam-
ples are buried in the sediments and the others are immersed in
water (Fig. 1). All these samples are corrosion-protected thanks to
10 sacrificial zinc anodes (one anode per structure). The zinc anodes
are provided by Bac Corrosion. All the impurities (Al, Cd, Fe, Pb
. . .) concentrations are less than 0.1% of the anode. The resulting
potential value is −1 V/AgAgCl, which is the common value used
for cathodic protection. In order to keep the potential at this value,
four manual cleaning operations of the anodes were necessary and
realised as soon as the potential was over than −0.9 V/AgAgCl (after
100, 200, 275 and 350 days). This loss of protection is due to an
excess of zinc oxides on the anodes [1]. The quantity of anodes
decreases during the experiment as two anodes (along with two
carbon steel structures) are removed at each sampling operation,
after 1, 3, 6, 9 and 12 months of cathodic protection [18]. This fre-
Table 1
Limit of detection and analyse of reference material LGC 6019 (water).
Element Limit of Certified values Measured
detection (␮g L−1 ) values (␮g L−1 )
(␮g L−1 )
Cr 6 0.78 ± 0.2 *

thanks zinc sacrificial anodes. This experiment was designed to Cu 2 15.4 ± 1.5 14 ± 1.3
study the cathodic protection and the calcareous deposit formation Pb 12 5.2 ± 0.3 *

on carbon steel samples immersed in natural seawater and buried in Zn 14 59.7 ± 2.5 63 ± 1.0
sediment. One anode per designed steel structure was used to main- *
Under the limit of detection.
tain the potential at −1 V/AgAgCl, which is the value commonly
used to maintain the cathodic protection. Theses structures were Table 2
designed to allow enough sampling (and deposit analysis) during Limit of detection and analyse of reference material HR1 (sediment).
the whole experiment. The mass of anodes to use is then depending Element Limit of Certified values Measured
of the metallic surface to protect. detection (␮g g−1 ) values (␮g g−1 )
A sequential extraction procedure was applied on sediment (␮g g−1 )
samples to evaluate the zinc mineralogical fractionation. Some Cr 0.8 126 ± 45 124 ± 1.6
other heavy metals (Cu, Cr, Pb and Zn) concentrations, in water Cu 2.8 79.9 ± 11.4 67.4 ± 1.6
and sediment samples, were also monitored to detect a possible Pb 2 139 ± 37 130 ± 3.8
influence of the cathodic protection on their distribution. Zn 2.5 1105 ± 173 1028 ± 13.9
 C. Rousseau et al. / Journal of Hazardous Materials 167 (2009) 953–958
quency is justified by the calcareous deposit evolution on the steel
surfaces that is monitored at the same time [18].
2.2. Seawater and sediments sampling and characterization
Seawater (SW) and sea sediments samples (SS) were periodically
collected and analysed from the very beginning of the experi-
ment (SW0 and SS0), then after 1 (SW1 and SS1), 3 (SW3 and
SS3), 6 (SW6 and SS6), 9 (SW9 and SS9) and 12 (SW12 and SS12)
months of cathodic protection. Sediments were collected in three
zones in the container: “superficial” sediments (in contact with
water), sediments closed to “steel” (15 cm from the water/sediment
interface) and “deep” sediments (30 cm from the water/sediment
interface). Additional samplings were also realised after the last
anodes cleaning operation (350 days), when only two anodes
remained immersed. Water and superficial sediments were then
collected after 1, 2, 3, 4 and 11 days after this cleaning operation.
After collection, sediments were air-dried at 30 ◦ C and stored
at 4 ◦ C in polypropylene bottles. Cu, Cr, Pd and Zn concentrations
were determined after microwave assisted acid digestion (HNO3
and HCl), by inductively coupled plasma atomic emission spec-
trometry (ICP-AES) (Varian Vista-MPX). These elements were also
quantified in seawater by ICP-AES analyses. The quality control of
ICP-AES data was assessed by the analysis of blank reagents and cal-
ibration standards prepared with commercially available solutions
(Varian solution standards). Accuracy of ICP-AES measurements
was determined using various certified reference materials (HR1
for sediment analyses and LGC 6019 for water). These data and the
limits of detection are presented in Tables 1 and 2. Other sediments
characterizations were also performed. The organic matter percent-
age was determined by loss-on-ignition at 375 ◦ C during 16 h [19].
The calcium carbonate rate was evaluated by the CO2 volume free
method after acid dissolution. The nature of clays was characterized
by X-ray diffraction (Philips, PW 3040/00 X’Pert MPD/MRD).
Sediments were also leached by an optimized sequential chem-
ical extraction procedure [6,7]. This procedure selectively and
efficiently dissolves all the chemical constituents of the sediments,
in the following order: F1: water soluble (released by ultrapure
water), F2: exchangeable (extracted with a magnesium nitrate
solution), F3: acido-soluble (leached by an acid/acetate buffer),
F4: reducible (extracted with hydroxyl ammonium, oxalic acid
and ascorbic acid), F5: oxidable fractions (released by hydrogen
peroxide-ammonium acetate extraction) and F6: sum of all labile
5
fractions ( i=1 Fi ).
3. Results
3.1. Heavy metals (Cu, Cr, Pb and Zn) concentrations in seawater
In Table 3 are presented the copper, chromium, lead and zinc
concentrations (mg L−1 ) in the various seawater samples. The aver-
age values observed by Brown et al. [3] in open ocean are also
reported.
Table 3
Cr, Cu, Pb and Zn concentration (mg L−1 ) analysed in the seawater samples and
average values in open ocean according to Brown et al. [3].
Cr Cu Pb
SW0 0.04 0.00 0.07
SW1 0.06 0.00 0.06
SW3 0.05 0.00 0.04
SW6 0.05 0.00 0.08
SW9 0.04 0.00 0.04
SW12 0.09 0.00 0.13
Open ocean 3 ×10−4 1 ×10−4 2 ×10−6
955
For all the reported elements, the levels were superior to the
values proposed by Brown et al. for open ocean [3]. This was not sur-
prising as the water used in this experiment was sampled near the
shore and is probably contaminated by various human activities.
Along the experiment, no significant concentration variation
was observed for any of the elements analysed, except for zinc,
which presented an important increase during the first months of
the experiment.
The zinc initial concentration was 0.04 mg L−1 . This level is high
if compared to the average values generally observed in open ocean
(Table 3) but is not unusual in harbour. Indeed, Bird et al. reported
values up to 0.03 mg L−1 in south coast of England harbours [2].
After 1 month of cathodic protection, an important increase
of zinc concentration was noticed as the concentration value
(SW1: 1.09 mg L−1 ) was about 30 times more than the initial one
(SW0: 0.04 mg L−1 ). This increase was undoubtedly correlated to
dissolution of the 10 zinc anodes used to apply the cathodic
protection (reaction (4)). Indeed, the first month of experiment
corresponded to the cathodic protection establishment, when the
current demand, and so the anode dissolution, are both at their
higher rate.
These results differ from those observed by Leleyter et al. [16],
which presented no significant increase of the water zinc concen-
tration after 1 month of cathodic protection, despite, the dissolution
of zinc anodes is recognized to contribute to the input of metals to
coastal waters, as shown by Bird et al. [2], Wagner et al. [20] or inside
the ballast tanks shown by Jelmert and Van Leeuwen [21]. Leleyter
et al. [16] values might result from an initial zinc water contami-
nation which could dissimulate the impact of the sacrificial anodes
dissolution on the seawater.
In the present experiment, this important zinc contamination is
only observed during the first month. Indeed, a regular decrease of
the water zinc concentration was observed (SW3: 0.48 mg L−1 to
SW12: 0.24 mg L−1 ) during the following months (Table 3), except
for the 9 months sampling, for which a low increase, compared to
the previous sampling, is detected (SW9: 0.71 mg L−1 ).
Various hypotheses could explain these results. First, after 3
months, then 6 months, the current demand is reduced of about 90%
[18]. This decrease results from the calcareous deposit formation on
the protected structure surface, which limits the cathodic (on struc-
tures) and anodic (on anodes) reactions: the anodes dissolution is
then reduced too, which limits the zinc input into water. Moreover,
at each collection time, two anodes were removed from the tank
[18]. Then, after 3 months and 6 months, respectively only eight
and six anodes remained immersed, which contributes to lower the
release of zinc into water. The water renewal also limits the increase
of water zinc concentration by a dilution effect. Furthermore, as
previously described, exchange reaction between water and solid
phases (suspended matters, sediments) can occur. For instance, at
pH 8.2, when Zn2+ concentration exceeds 1.16 mg L−1 , it can precip-
itate as Zn(OH)2 [21], which then influences the apparent variation
of water zinc concentration.
A cleaning operation was performed on the anodes 5 days before
the 9 months sampling (t: 275 days). During this operation, the zinc
oxides layer is removed from the anodes surface, but cannot be
removed from the tank and is then dispersed into the experimental
medium. This obviously induces an important increase of zinc level
in the liquid and solid phases, as this layer is probably partly dis-
Zn solved in the water. This explains the high value measured in water
0.04 5 days after this cleaning (SW9: 0.71 mg L−1 ).
1.09 At the end of the experiment, the water contamination by
0.48 zinc coming from anode dissolution is actually significant as, after
0.52
12 months, the zinc concentration observed (SW12: 0.24 mg L−1 )
0.71
0.24
is more than six times higher than the initial value (SW0:
0.04 mg L−1 ), despite partial water renewal and various phenomena
5 ×10−4
that tend to lower water zinc levels.
956 C. Rousseau et al. / Journal of Hazardous Materials 167 (2009) 953–958

Table 4
Zinc concentration in water (mg L−1 ) and in superficial sediments (␮g g−1 ) after
cleaning of the two remaining anodes.

Delay following Zinc concentration in Zinc concentration in

cleaning step (day) water (mg L−1 ) superficial sediments
(␮g g−1 )

0 0.33 830
1 0.80 1490
2 1.02 2700
3 1.03 2670
4 1.20 1780
11 0.24 500

The impact of the anode cleaning operation was also evaluated

at the end of the experiment (350 days) before the last water and
sediment collection (SW12 and SS12), when only two anodes were
still immersed. The results are presented in Table 4. During the first
Fig. 2. Total zinc concentration (␮g g−1 ) in sediments, and zinc concentration in
4 days following the cleaning operation, the zinc concentration pro- seawater values (mg L−1 ) into circles.
gressively increases in water (from 0.33 mg L−1 to 1.20 mg L−1 ). This
variation can be due to the progressive dissolution of some zinc
solid particles that covered the anode surface (i.e., zinc oxides layer, these sediments were higher than the baseline values proposed by
[1]). However, 11 days after the cleaning operation, the zinc concen- Stevenson for North Atlantic non-polluted sediments [22]. These
tration is back to its initial value (0.33 mg L−1 ), suggesting that the sediments can then be considered as moderately polluted by Cu
anode cleaning step only induces a very punctual water contam- and Pb. Their concentrations remain stable all along the experiment
ination, by enhancing the zinc solid compounds dissolution. This and at the different depth observed. The cathodic protection had no
contamination is rapidly attenuated by the dilution effect and/or influence on these elements level onto the sediment.
zinc sorption phenomenon onto sediments. The zinc total concentrations in sediments are presented on
It is important to note that all the zinc concentrations observed Fig. 2, in order to visualise zinc spatial and/or temporal evolution.
in this experiment (from SW0 to SW12) exceed the OSPAR Conven- Variation of zinc content was only observed in the surface sed-
tion provisional ecotoxicological assessment criteria for seawater iment. The concentration measured in the “steel” samples (near
(5 × 10−3 mg L−1 ) [4]. Moreover, we can conclude that the sacrifi- structures) and “deep” samples (30 cm from the interface) show
cial anodes used in our experimental conditions induce a significant no significant variation, then the discussion will focus on results
increase of the water zinc concentration. obtained for the superficial sediments. Variations of sediments zinc
content versus time are noticed, following more or less the same
3.2. Heavy metals (Cu, Cr, Pb and Zn) concentration in sediment pattern observed for water (water values presented into circles on
Fig. 2).
33% of calcium carbonate and 4% of organic matter were mea- An important level increase is observed after the first month
sured in the dried sediments used in the experiment [18]. The high (from 138 ␮g g−1 (SS0) to 757 ␮g g−1 (SS1), Table 5 and Fig. 2).
percentage of calcium carbonate is due to the erosion of marine This can probably be explained by some zinc sorption phenom-
shells collected with sediments. The X-ray diffraction analyses indi- ena onto the surface sediment or by the formation of zinc solid
cate the presence of different clays: kaolinite, illite, chlorite, and compounds (which settled down). This can be correlated to the
interstratified layers of illite and chlorite. These detected clays are important water zinc content increase previously described. During
generally present in marine sediments of the pelagic zone [3]. the 5 following months, the zinc level progressively decreases (from
Heavy metals (Cu, Cr, Pb and Zn) concentrations in sediments SS3: 537 ␮g g−1 to SS6: 153 ␮g g−1 ), and is back to its initial value
are presented in Table 5. Copper and lead contents determined in after 6 months. This can only be explained by a desorption and/or
redissolution process of zinc associated to the sediment, towards
the water phase, as deeper sediment content remains unchanged.
Table 5
Cr, Cu, Pb and Zn concentration (␮g g−1 ) analysed in the sediments samples and Moreover, such a phenomenon could contribute to maintain or
average values in the North Atlantic continental seabed according to Stevenson [22]. slightly increase zinc water content from SW3 to SW6, as it has
been noticed (Table 3, Fig. 2). This suggests that the sediments can
Cr Cu Pb Zn
buffer the pollution: when the water is contaminated, the sorption
SS0 superficial 36 26 37 138
phenomenon reduced the water levels. But then, the phenomenon
SS0 deep 35 24 37 126
SS1 superficial 39 26 38 757
being reversible, sediments become a pollution source that can
SS1 steel 40 27 40 135 increase water metal level.
SS1 deep 41 25 38 142 After 9 months, a very important increase of zinc level is
SS3 superficial 47 20 41 537 observed in the superficial sediments (SS9: 750 ␮g g−1 ) compared
SS3 steel 41 21 34 106
to the previous sampling (SS6: 153 ␮g g−1 ). As for water, this value
SS3 deep 46 21 35 115
SS6 superficial 42 18 36 153 might probably be attributed to the anode cleaning operation,
SS6 steel 46 18 38 124 realised 5 days before. As previously noticed, zinc solid compounds
SS6 deep 46 19 35 127 are probably released during this operation, being partly dissolved
SS9 superficial 46 18 38 750 and/or settled down. This additional zinc is then co-analysed with
SS9 steel 45 21 38 142
SS9 deep 53 19 40 133
the sediment and cannot be discriminated from the zinc actually
SS12 superficial 43 18 34 504 sorbed onto the sediment phase.
SS12 steel 49 19 35 129 Thus, superficial sediment samples were collected (as for water)
SS12 deep 47 20 38 133 at the end of the experiment to better evaluate the anode clean-
Stevenson [22] 55 15 11 57
ing impact. Zinc level increases during the first 2 days following
 C. Rousseau et al. / Journal of Hazardous Materials 167 (2009) 953–958
Fig. 3. Quantity of zinc, in ␮g g−1 , leached from the different mineralogical fractions
of the superficial sediments (residual = total − F6).
the cleaning (from 830 ␮g g−1 to 2700 ␮g g−1 , Table 2). How-
ever, 11 days after the cleaning operation, the zinc concentration
(500 ␮g g−1 ) is back (or inferior) to the value determined before
the cleaning (830 ␮g g−1 ). The zinc solid compounds or the sorbed
zinc appear to be rapidly solubilized or desorbed into water. Finally,
anode cleaning operation has a limited influence on the sediment
contamination.
At the end of the experiment, the zinc concentration (SS12:
500 ␮g g−1 ) is about three times higher compared to its initial value
(SS0: 138 ␮g g−1 ), in spite of a limited anode dissolution (cathodic
protection being stable) and a limited number of remaining anodes
(two at this moment).
In our experimental conditions, the sacrificial anodes induce
a significant increase of the sediment zinc content. These results
are in agreement with other studies on zinc contamination by sac-
rificial anodes [2,16], which also revealed a superficial sediment
contamination. In fact, Bird et al. realised a depth profile of zinc
in sediment, in a semi-enclosed marina on the south coast of Eng-
land [2]. This zinc profile presents a sub-surface maximum zinc
content (225 ␮g g−1 ) at the water/sediment interface and less than
150 ␮g g−1 at 20 cm from the interface.
3.3. Zinc partitioning in superficial sediments
To estimate heavy metal mobility and bioavailability in sed-
iments, the superficial sediments samples were leached by an
optimized sequential chemical extraction procedure [6,7]. As for
their total concentrations in sediments, no variation was observed
for Cu, Cr and Pb fractionation scheme all along the experiment and
in the three zones of the container [18]. The cathodic protection had
no influence on the mineralogical fractionation of these elements.
The situation is quite different for zinc, for which significant
variation was detected in the superficial sediments (whereas zinc
distribution remained stable in “deep” and “steel” samples). Then,
the discussion will focus on the superficial sediments results. The
zinc quantity (␮g g−1 of dry sediment) leached from the different
mineralogical fractions is represented in Fig. 3; percentages val-
ues ( = ratio with the total concentration) are also calculated and
represented in Fig. 4.
Zinc is initially mainly scavenged in two fractions: the most
important part is present in the reducible fraction (F4), with
60 ␮g g−1 (42%) and in the acido-soluble fraction (F3), with
30 ␮g g−1 (23%). This kind of distribution is not unusual for zinc
and has been reported in various studies [2,11,15–17].
After 1 month, zinc is mainly associated to the acido-soluble (F3)
and reducible (F4) fractions. The zinc quantity in these two fractions
has increased (F3: 310 ␮g g−1 ; F4: 228 ␮g g−1 ) as a consequence of
957
Fig. 4. Distribution of zinc, in %, in the different mineralogical fractions of the super-
ficial sediments (residual = total − F6).
the total zinc content increase, as previously noticed (Fig. 2; Sec-
tion 3.2). But, contrary to the initial fractionation and according to
Leleyter et al. [16], the dominant fraction is the acido-soluble one
(41%), followed by the reducible (30%) fraction.
It is important to note that, after 1 month of experiment, no zinc
was leached by water (water soluble fraction F1: 0%). This suggests
that the additional zinc-associated sediment (and co-analysed),
resulting from contamination by the anode dissolution, is either
actually sorbed onto the sediment and/or result from the settle
down of some zinc solid compounds, formed on the anode surface
layer, that are not water soluble.
After 3 and 6 months, the zinc quantity leached by the sequen-
tial extraction (F6) decreases, like the total zinc content in sediment.
However, after 3 months, the zinc quantity decreases in F3 (from
310 ␮g g−1 to 230 ␮g g−1 ) whereas it stays stable in F4 (about
220 ␮g g−1 ), suggesting that the decrease of the total zinc content
is due to the leach by the seawater of the most labile zinc (frac-
tion F1 to F3). This trend is confirmed after 6 months, with still
reduced acido-soluble (F3: 70 ␮g g−1 ) and reducible (F4: 70 ␮g g−1 )
fractions, and without any increase of the other ones.
After 12 months, a “new” zinc contamination was detected and
attributed to the anode cleaning operation, performed 5 days before
the final sampling (see Section 2.2). Compared to the previous sam-
pling, higher quantity of zinc were noticed, with more zinc present
in the acido-soluble fraction (F3: 141 ␮g g−1 ) and much more zinc
in the reducible fraction (F4: 170 ␮g g−1 ). This quite important rise
of the reducible fraction might be correlated to the release of some
zinc compounds, as zinc oxides which are reducible compounds.
Furthermore, results obtained on SS12 were compared to those
determined on SS3, as these two samples presented quite the same
total zinc content (respectively 500 ␮g g−1 and 537 ␮g g−1 ). How-
ever, zinc fractionation is quite different in these two samples: the
total labile fraction (F6) is significantly lower for the sample SS12,
after the anode cleaning operation (F6: 63%) compared to the SS3
samples (F6: 84%). This suggests that zinc chemical speciation is
responsible for such difference, as the zinc species, resulting from
the anodes cleaning (i.e., ZnO, see Section 3.1) appear clearly less
available than the dissolved Zn(II) species, liberated in the solution
by the anode oxidation (reaction (4)).
4. Conclusion
The use of sacrificial anodes to apply cathodic protection induces
a significant water contamination by Zn2+ ions. But when the Zn2+
concentration exceeds the solubility threshold (1.16 mg L−1 , at pH
8.2), this excess of free ions is consummated by precipitation (i.e., as
Zn(OH)2 ) or by complexation [21]. Zinc could be also sorbed and/or
958 C. Rousseau et al. / Journal of Hazardous Materials 167 (2009) 953–958
precipitated onto the surface sediment. Zinc, coming from this per-
manent anode dissolution, is mainly scavenged, in the sediments,
into the acido-soluble fraction. This fraction is usually related to
metal bound to carbonate compounds. The contaminated sedi-
ments then appear as a secondary pollution source, as zinc can be
remobilized towards water, depending on possible modifications
of the physicochemical parameters, i.e., pH changes, or zinc water
concentration variation. When this concentration becomes inferior
to the solubility threshold, for example after a high tide exposition
or during harbour dredging operations, the zinc associated to solid
phases can be released into water. Such exchange between the sed-
iment phase and the water column can induce to potential toxic
effect under new environmental conditions.
The anode cleaning operations (necessary to maintain an effi-
cient protection under controlled conditions and which naturally
occurs under real conditions), also induces water and superficial
sediments contamination. But this phenomenon is rapidly attenu-
ated. However, the chemical speciation of the liberated zinc might
be quite different from the zinc speciation resulting from the sacrifi-
cial anodes dissolution. This is in agreement with the mineralogical
fractionation results, which indicate that zinc, coming from the
anodes cleaning is less available that the one resulting from the
anode dissolution. Indeed, the zinc, coming from the anodes clean-
ing, such as zinc oxides, is mainly scavenged into the reducible
fraction. Then the environmental impact of zinc coming from zinc
sacrificial anodes, depends on its origin (anode cleaning/anode oxi-
dation), but these two effects add up.
This study provides information on the potential mobility of zinc
in marine sediments, which depends on its chemical speciation.
Under the developed experimental conditions (basin closed with
low renewal), zinc contamination of water and surface sediments
is higher than expected under environmental conditions, but these
semi natural conditions can simulate enclosed harbour areas, which
are not exposed to the tide. The concentrations observed are poten-
tially toxic for the environment, especially for the filter feeding
organisms, and could cause the whole food chain contamination.
Acknowledgements
This research was supported by the European Regional Devel-
opment Fund (ERDF), the Conseil Régional de Basse Normandie
and the Conseil Général de la Manche. The authors acknowledge
the Laboratoire de Morphodynamique Continentale et Côtière of
Caen-Basse Normandie University for their contributions to the
sediments characterization.
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