Environmental Pollution 157 (2009) 371–376

Contents lists available at ScienceDirect

Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Leaching of copper and zinc from spent antifouling paint particles

Nimisha Singh, Andrew Turner*
School of Earth, Ocean and Environmental Sciences, University of Plymouth, Drake Circus, Plymouth PL4 8AA, UK

Copper and zinc are readily leached from particles of spent antifouling paint under a range of environmental conditions.

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

Article history: Leaching of Cu and Zn from a composite of spent antifouling paint particles, containing about 300 mg g1
Received 24 June 2008 and 110 mg g1 of the respective metals, was studied in batch experiments. For a given set of simulated
Received in revised form 1 October 2008 environmental conditions, release of Cu was independent of paint particle concentration due to
Accepted 3 October 2008
attainment of pseudo-saturation, but Zn was less constrained by solubility effects and release increased
with increasing particle concentration. Leaching of Cu increased but Zn decreased with increasing
Keywords:
salinity, consistent with mechanisms governing the dissolution of Cu2O in the presence of chloride and
Antifouling paint particles
Zn acrylates in the presence of seawater cations. Because of complex reaction kinetics and the presence
Leisure boats
Copper of calcium carbonate in the paint matrix, metal leaching appeared to be greater at 4  C than 19  C under
Zinc many conditions. These findings have important environmental and biological implications regarding the
Leaching deliberate or inadvertent disposal of antifouling paint residues.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction non-active) constituents from spent antifouling paint residues.

Antifouling paint is applied to the hulls of boats and to other
submerged structures to prevent colonisation by various organ-
isms, including microalgae, macroalgae and invertebrates. Most
contemporary antifouling formulations employ an active pigment
and a variety of organic or organo-metallic booster biocides which
are embedded in, or linked with, an organic matrix. Cuprous oxide
(Cu2O) is the usual choice of pigment, although Cu(I) thiocyanate
and Zn(II) oxide are also commonly employed.
Critical to the performance and lifespan of an antifouling
application are the leaching rates and toxicities of the pigments and
co-biocides. Leaching rate is controlled by both the dissolution
kinetics of the active constituents and the mechanisms by which
these constituents are exposed to the aqueous medium. Standard
laboratory methods, typically based around painted, rotating
cylinders immersed in artificial seawater, exist for measuring the
release rates from single, well-defined antifouling applications
(Finnie, 2006). Results of such tests indicate a dependence on the
precise physico-chemical properties of the formulation, hydrody-
namics and a variety of environmental factors. The latter include
temperature, salinity, pH and the presence of biofilms (Valkirs et al.,
2003).
Largely unknown, however, are the physical and environmental
factors that control the extents and rates of leaching of active (and
Such particulates are not only generated during the regular main-
tenance of boats (Page et al., 1996; Tolhurst et al., 2007; Turner
et al., 2008) but also readily flake off structures, including aban-
doned and grounded vessels, in situ (Haynes and Loong, 2002;
Negri et al., 2004). Fragments of coloured paint are visible in
sediment in the vicinity of boatyards, where leaching is likely to
contribute to elevated concentrations of many chemical constitu-
ents in the interstitial environment and the overlying water
column. Finer, less visible particulates, generated during sanding or
blasting of boat hulls, are predicted to leach more rapidly. More-
over, particles of this size have the potential to be transported over
greater distances and be exposed to a wider range of environmental
conditions.
In this study, we examine the leaching of the principal metallic
biocidal components, Cu and Zn, from a composite of antifouling
paint fragments collected from a marine leisure boat maintenance
facility. Experiments are conducted in batch reactors under
controlled but varied conditions representative of estuaries and
coastal waters. We employ natural seawater and river water rather
than artificial samples, thereby empirically accounting for the
effects of dissolved organic matter and, potentially, biofilm
formation on the leaching process.
2. Materials and methods

Before use, equipment for sampling and experimental work was soaked in 10%
HCl for at least 24 h and subsequently rinsed in distilled water. Unless otherwise
* Corresponding author. Tel.: þ44 1752 584750; fax: þ44 1752 585710. stated, reagents employed were of analytical grade or better, and were purchased
E-mail address: aturner@plymouth.ac.uk (A. Turner). from Sigma–Aldrich, Fluka, VWR or Fisher Scientific.

0269-7491/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2008.10.003
372 N. Singh, A. Turner / Environmental Pollution 157 (2009) 371–376
2.1. Sample collection and processing
Fragments of boat paint were retrieved by hand from the hard-standings of
a large (>100 berth) marine leisure boat facility in Plymouth during April 2007
when hull maintenance was taking place. Although the precise sources and ages of
the fragments are unknown, the net sample is representative of the signature of
particulate contamination arising from the general, contemporary practice of leisure
boat maintenance. In the laboratory, extraneous particulates (e.g. grit, macroalgae)
were removed before the fragments were ground with a pestle and mortar, a process
aided by the occasional addition of a few millilitres of liquid nitrogen. The ground
composite was then sieved through a succession of Nylon meshes to isolate the
<63 mm and 63–180 mm size fractions. Fractionated samples were stored in the dark
in individual wide-necked polyethylene bottles.
River water was collected from the Plym, SW England, in 5 L polyethylene
carboys as required, and on three occasions within a three-week period, during
November 2007. The Plym is a low alkalinity river that drains about 80 km2 of
protected area of moorland, and typical concentrations of dissolved organic carbon
(DOC) and chloride at this time of year are about 2 mg L1 and 25 mg L1, respec-
tively (Turner et al., 2006). In the laboratory, samples were vacuum filtered through
0.45 mm cellulose nitrate membranes (Whatman) and subsequently stored in clean
polyethylene bottles at 4  C in the dark. The pH and conductivity of the filtered
samples (measured at room temperature) ranged from 6.6 to 6.9 and 69 to
77.1 mS cm1, respectively. Seawater, having been collected in bulk from Plymouth
Sound at high water (salinity ¼ 34; pH ¼ 7.7; DOC ¼ 3.0 mg L1), was available on tap
in the laboratory. Before use, a sufficient volume was filtered through 0.45 mm as
above.
2.2. Paint composite characterization
Total digestion of metals in the paint composite was achieved using aqua regia.
Triplicate 5 mg aliquots of each size fraction were accurately weighed into individual
50 mL Pyrex beakers. Five mL of three parts HCl to one part HNO3 were added to
each beaker, and after about 1 h the contents were covered with watch glasses and
heated on a hot plate to about 75  C for a further 2 h. The cooled contents and Milli-
Q water rinsings were transferred to individual 25 mL Pyrex volumetric flasks and
diluted to mark with 0.1 M HNO3. Accuracy was evaluated from triplicate digestions
of estuarine and harbour sediments certified for metal concentrations available to
aqua regia (LGC 6137 and LGC 6156, respectively; Laboratory of the Government
Chemist, Teddington, UK). Procedural blanks were performed likewise but in the
absence of solids.
Organometallics were solvent extracted from the paint composite (Thomas
et al., 2000). Triplicate 50 mg portions of each size fraction were weighed into
individual Pyrex beakers and 30 mL aliquots of a 1:1 mixture of dichloromethane–
ethylacetate were added. Beakers were covered with Al foil and agitated on a lateral
shaker at about 100 rpm at room temperature for about 2 h. The contents were then
sonicated for 10 min before being centrifuged at 2100 g for 15 min. Ten millilitres of
the supernatants were transferred to clean beakers and the contents evaporated to
dryness in a laminar flow hood for about 24 h. Residues were redissolved in 5 mL of
0.1 M HNO3 and transferred to 10 mL volumetric flasks where they were diluted to
mark with Milli-Q water. Procedural blanks were undertaken likewise but in the
absence of paint particles.
Digests and extracts were analyzed for Cu and Zn by inductively coupled plasma-
optical emission spectrometry (ICP-OES) using a Varian 725 ES (Mulgrave, Australia)
calibrated with mixed, acidified standards and internally standardised with yttrium.
Analysis of the digests of the reference sediments revealed w/w concentrations of
Cu and Zn that were within 10% of the corresponding certified values.
The specific surface area of about 200 mg of each size fraction of the paint
composite was determined by multipoint BET nitrogen adsorption at 77 K using
a Micrometrics Gemini 2360.
2.3. Leaching experiments
The leaching of Cu and Zn from each size fraction of the paint composite was
studied in a series of batch experiments under conditions that we have previously
adopted for metal–sediment adsorption studies (Turner et al., 2006). Thus, we added
25 mg of paint particles to 220 mL of filtered water in a 500 mL high density poly-
ethylene beaker and the covered contents were agitated via a plastic-coated
magnetic stirrer for 120 h. Experiments were undertaken at room temperature
(19  2  C) and in a refrigerator (4  1  C, and with regular, manual agitation), over
a range of different salinities, created by mixing filtered river water and seawater in
different proportions, and in the presence of variable concentrations of humic
substances, added from a concentrated solution of Acros Organics humic acid sodium
salt (60% humics by weight). A few experiments were performed using different
quantities of paint particles in order to evaluate any effects of particle concentration
on metal leaching. The pH of each reactor, monitored throughout using a Jenway
3305 meter, was found not to deviate from the original value by more than 0.2 units.
At the end of the incubations, 20 mL samples were vacuum filtered through
0.45 mm and three 5 mL aliquots were added to individual Sterilin tubes and acidi-
fied with 200 mL of concentrated HNO3. To examine the kinetics of metal release,
subsampling was performed throughout the 120 h period in some cases. Copper and
Zn were determined in filtered subsamples by ICP-OES as above, and corrected for
corresponding background concentrations in river water, seawater or mixtures
thereof (typically <10 mg L1). Analysis of acidified filtrates of river water and
seawater to which 2.5 mg L1 of Cu and Zn had been added from standard solutions
(in the absence of paint particles) revealed no adsorptive or precipitative loss of
metal during the incubations.
3. Results and discussion
3.1. Sample characteristics
Concentrations of Cu and Zn in both size fractions of the paint
composite are given on a dry weight basis in Table 1. For a given
metal, concentrations were statistically indistinguishable between
the two size fractions (p > 0.05 according to a two-sample t-test),
suggesting that grinding and sieving afford a suitable means of
sample homogenisation and that the efficacy of aqua regia
digestion is insensitive to paint particle size. The results are in
quantitative agreement with the composition of contemporary,
copper-based antifouling formulations (Yebra et al., 2004) and are,
therefore, consistent with a self-polishing mechanism of leaching
in situ. Since organometallics were detected in the composite, we
surmise that booster co-biocides, such as Cu and Zn pyrithione,
Ziram and Zineb, were also present.
Specific surface areas of both fractions of the paint composite,
also shown in Table 1, are an order of magnitude greater than
geometric surface areas based on spherical grains of a median
diameter (32 or 117 mm) and a density of 2 g cm3. This suggests
that the ground paint particles possess considerable microporosity.
Despite differences in specific surface area, hence degrees of
pigment exposure to the aqueous medium, leaching of metal from
both size fractions of the paint composite was similar. With respect
to Cu at least, this effect may be attributed to attainment of pseudo-
saturation in our experiments (see below). Hereafter, we focus on
results for the <63 mm fraction, which is more representative of the
particle size distribution generated by hydroblasting of boat hulls
(Schratzberger et al., 2002).
3.2. Influence of paint particle concentration and metal solubility
on metal leaching
An important practical and environmental consideration with
regard to metal leaching is the ratio of paint particle mass to
solution volume (i.e. particle concentration). Initial experiments
involved addition of different quantities of paint composite to the
same volume of water under otherwise identical conditions.
A selection of the results is shown in Fig. 1 in terms of both the w/v
concentration in the aqueous phase and the percentage of total
metal that had leached out from the original composite.
With respect to Cu, and for a given set of environmental
conditions, the w/v concentration released was constant over the
range of particle mass added. Concentrations in seawater exceed
the solubility of Cu based on inorganic speciation considerations
(about 0.5 mg L1 at pH 8 and 25  C; Woods Hole Oceanographic
Institute, 1952), yet no discolouration or precipitation, such as blue-
green basic copper carbonate, was observed in the experiments.
Table 1
Characteristics of the two size fractions of the boat paint composite (on a dry mass
basis). The standard deviation about the mean of three independent determinations
is given for Cu and Zn.
<63 mm 63–180 mm
Cu, mg g1 (Total) 311,200  20600 284,300  1790
(Organometallic) 463  61 367  59
1
Zn, mg g (Total) 114,100  7660 108,300  4870
(Organometallic) 1310  73 1660  234
Specific surface area, m2 g1 1.52 0.79
 N. Singh, A. Turner / Environmental Pollution 157 (2009) 371–376 373

3 16

12

[Cu], mg L-1
2

[Cu], %
8

1
4

0 0
0 100 200 300 400 500 0 100 200 300 400 500
Cp, mg L-1 Cp, mg L-1
3 16

12
[Zn], mg L-1

[Zn], %
8

1
4

0 0
0 100 200 300 400 500 0 100 200 300 400 500
Cp, mg L-1 Cp, mg L-1

Fig. 1. Release of Cu and Zn from the <63 mm fraction of the paint composite after 120 h incubation as a function of paint mass to water volume (Cp) in river water at 4  C (6) and
19  C (:) and in seawater at 4  C (,) and 19  C (-). Results are shown in terms of both aqueous concentration and the percentage of total metal on a dry mass basis. Error bars
represent the standard deviation about the mean of three determinations.

Relatively high aqueous metal concentrations in our experiments
can be attributed, partly, to the formation of soluble (or colloidal)
organic complexes, and to the dissolution of organometallic booster
biocides, whose solubilities are on the order of a few mg L1 (Omae,
2003). However, the effect was also apparent on addition of
2.5 mg L1 of ionic Cu to filtered seawater in the absence of paint
particles, and has been observed independently in the absence of
aqueous organic matter and organometallics (Woods Hole Ocean-
ographic Institute, 1952).
The causes of ‘‘pseudo-saturation’’, in which apparent saturation
occurs at a concentration above that predicted from thermody-
namics, are not fully understood. However, since the effect appears
to limit the solubility of Cu in our experiments, it has important
consequences. Thus, firstly, the percentage of Cu released from the
paint composite increases with decreasing particle concentration,
and secondly, leaching of Cu is relatively insensitive to particle size,
hence surface area of pigment exposed to the aqueous medium.
Surface area is, however, responsible for the considerable discrep-
ancies in Cu leaching rates from ground paint particles and from
painted panels in rotary tests where pseudo-saturation is not
approached. For example, we observed up to 15% leaching of Cu
from the paint composite in 120 h, whereas Fay et al. (2005) report
about 1% release from a variety of acrylic copolymer paints
immersed in artificial seawater for a period of 36 weeks.
Regarding Zn, an increase in release is observed with increasing
particle concentration such that an inverse relationship between
percentage of Zn leached from the composite and particle
concentration is partly offset. Because of the greater solubility of Zn
compounds (e.g. Zn(OH)2 ¼ 16.5 mg L1), true or pseudo-saturation
is only likely to be attained with respect to co-leached resinic
groups, and at concentrations in excess of those reported in the
present study (Yebra et al., 2005).
3.3. Leaching kinetics and dependence on salinity and temperature
The time-dependence of metal release from the paint composite
was examined under different environmental conditions at the
default particle concentration of about 100 mg L1. The results,
shown in Fig. 2, are complex and appear to be dependent on the
experimental conditions and the metal. With respect to Cu, in both
river water and seawater at 19  C there is evidence of one or more
‘‘spikes’’ in concentration, followed by a period of relaxation to
steady state or pseudo-saturation. At 4  C, however, concentrations
appear to exhibit more of a continual increase throughout the time-
course. The latter distributions are characteristic of the leaching of
Zn under all experimental conditions.
The end-points of the time-courses are consistent with corre-
sponding results of experiments in which particle concentration
was altered (Fig. 1) and in which an estuarine gradient was simu-
lated by mixing river water and seawater (see Fig. 3). These
observations suggest that any effects engendered by compositional
variations in the end-members (e.g. river water sampled on
multiple occasions) are not sufficient to mask the general patterns
in metal mobilisation. With respect to the estuarine gradient,
concentrations of Cu released after 120 h incubation increase with
increasing salinity at both temperatures, but the increase was more
pronounced at 4  C. Accordingly, compared with Cu release at
19  C, release at the lower temperature is reduced in river water
and enhanced in seawater. For Zn, leaching is reduced from river
water to seawater at both temperatures, but release is greater at the
lower temperature at salinities of less than about 5.
3.4. Dissolution mechanisms
The mechanism by which cuprous oxide dissolves in seawater is
well documented (Howell and Behrends, 2006) and is partly
consistent with the observations above. Thus, with respect to
antifouling formulations, cuprous chloride complexes are formed at
the pigment front:
½Cu2 OðsÞ D HD D 2ClL 4 CuClL
2 D ½H2 O (1)
2L
2 D Cl 4 CuCl3
CuClL L
(2)
where reaction (1) is reversible but kinetically constrained, and
reaction (2) is reversible and instantaneous. In the presence of
374 N. Singh, A. Turner / Environmental Pollution 157 (2009) 371–376

3 3
SW RW

[Cu], mg L-1
[Cu], mg L-1
2 2

1 1

0 0
0 20 40 60 80 100 120 0 20 40 60 80 100 120
time, h time, h

4 4
SW RW

3 3

[Zn], mg L-1
[Zn], mg L-1

2 2

1 1

0 0
0 20 40 60 80 100 120 0 20 40 60 80 100 120
time, h time, h

Fig. 2. Time-dependent release of Cu and Zn from 114 mg L1 of the <63 mm fraction of the paint composite in seawater (SW) and river water (RW) and at 4  C (B) and 19  C (C).
Error bars represent the standard deviation about the mean of three determinations.

dissolved oxygen, univalent copper is rapidly oxidized to Cu2þ,
the principal biocidal constituent, in the leach layer. The toxicity
of Cu2þ is subsequently diminished through the formation of
inorganic and organic complexes and its adsorption to natural
surfaces (Meyer et al., 2007; Hatano and Shoji, 2008). Because
a dependence of Cu release rate on the concentration of both Hþ
and Cl is indicated by reactions (1) and (2), leaching is predicted
to increase with decreasing pH and increasing salinity (Kiil et al.,
2002). Thus, regarding our experimental results, despite an
increase in pH from river water to seawater and the presence of
dissolved organic matter throughout (see below), a rate depen-
dence on the square of chloride concentration ensures an
increase in Cu release is observed across the entire estuarine
gradient.
Equivalent information on the dissolution of ZnO in the pres-
ence of chloride is not available, although the following overall
reaction has been hypothesised (Yebra et al., 2007):
ZnOðsÞ D H2 O D 2ClL 4 ½ZnCl2L
4 D ½ZnðOHÞ3 D ½OH
L L
(3)
A dependence on the square of chloride concentration is not,
however, in agreement with greater leaching of Zn in river water
than in seawater. This suggests that a significant proportion of Zn in
the paint composite may occur in an alternative form. In many self-
polishing, acrylic- or rosin-based compounds, Zn (and sometimes
Cu) is released according to the following type of reaction (Yebra
et al., 2004):
RCOO—Zn—OOCRðsÞ D 2NaD 4 2RCOOL NaD ðaqÞ D Zn2D (4)
where RCOO represents carboxylate or acrylate and Naþ is an
indicative counter ion. Since this is (loosely) an ion exchange
mechanism, an increase in metal release with increasing salinity
might be predicted. However, consistent with our observations,
results of experiments involving a Zn-carboxylate of a synthetic rosin
compound indicate a reduction in release of metal with increasing
NaCl concentration (Yebra et al., 2005). This suggests that the
concentration of Naþ does not affect the dissolution rate of Zn,
provided its concentration is greater than that of other species
involved (e.g. OH), and that an increase in ionic strength may inhibit
the diffusion of certain ionic solutes from the paint matrix.

3 1.5
[Cu], mg L-1

[Zn], mg L-1

2 1.0

1 0.5

0 0.0
0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35
salinity salinity

Fig. 3. Release of Cu and Zn from 114 mg L1 of the <63 mm fraction of the paint composite after 120 h incubation as a function of salinity and at 19  C (C) and 4  C (B). Error bars
represent the standard deviation about the mean of three determinations.
 N. Singh, A. Turner / Environmental Pollution 157 (2009) 371–376
Given the temperature dependence of transport processes and
of chemical reactions and dissolution rates involving metals, the
mechanisms discussed above appear to be at odds with an increase
in the release rate of Cu and Zn observed at the lower temperature
under a broad range of conditions. A possible explanation for this
anomalous behaviour is that biocide leaching is partly controlled by
the dissolution of calcium carbonate, a process that displays an
inverse dependence on temperature. Calcium carbonate may be
present at the paint particle surface in the form of biodeposits or
may be a component of the matrix itself as an extender pigment.
Paint fragments that we have analyzed by scanning electron
microscopy have failed to reveal calcareous biodeposition at the
surface, but clearly demonstrate calcium carbonate in the matrix of
most samples (Singh and Turner, in press). With respect to Cu, at
least, it is also possible that the temperature dependence is related
to reaction kinetic constraints during the time-course of the
experiments. Thus, it is reasonable to assume that the spikes in Cu
concentration observed at 19  C are the result of some adjustment
in aqueous metal speciation, partial (re-)precipitation of relatively
insoluble species, and adsorption of metal to chemically or bio-
logically altered sites on the paint particle surface (including algi-
nate functional groups of bacterial slimes). At 4  C, these
mechanisms proceed more slowly such that, after 120 h, the
shoulder of an equivalent but delayed peak, rather than the ensuing
period of relaxation and pseudo-saturation, is sampled.
3.5. Effects of dissolved organic matter on metal leaching
Relatively high concentrations of aqueous Cu and Zn in our
experiments (or pseudo-saturation in the case of the former) were
attributed, in part, to the formation of soluble organic complexes.
Ligands could be co-leached from the paint matrix, or pre-exist in
the filtered water samples. Sandberg et al. (2007) found that up to
20% of Cu released from a variety of contemporary antifouling
formulations immersed in artificial seawater was electrochemically
inactive, and suggested that strong complexation by organic
substances concurrently dissolved from the paint matrix was
responsible. Significantly, some of these substances, like thio-
carbamates, may combine with metals to form lipophilic complexes
(Voulvoulis et al., 1999). Many naturally occurring dissolved
organics, including humic and fulvic substances, amino acids, and
biological exudates, readily bind with Zn and, in particular, Cu,
whose speciation in most aquatic environments is dominated by
organic complexation (Xue et al., 1996).
The role of complexation on metal release from the paint
composite was evaluated in experiments in which humic
substances were added to the suspensions. The results, shown in
Fig. 4, reveal that the polyelectrolyte enhances release of Cu and Zn
in fresh water and, in most cases, seawater, but not in proportion to
the quantity added. Since humics and other natural organics bind
1.5
[Zn], mg L-1
[Cu], mg L-1
1.0
0.5
0.0
0 2 4 6
[HA], mg L-1
Fig. 4. Release of Cu and Zn from 114 mg L1 of the < 63 mm fraction of the paint composite after 120 h incubation at 19  C as a function of concentration of humic acid (HA) added
to river water (:) and seawater (-). Error bars represent the standard deviation about the mean of three determinations.
375
with both Cu(I) and Cu(II), often strongly (Leal and van den Berg,
1998; Kogut and Voelker, 2001), their effects on leaching of this
metal are predicted to be, qualitatively, similar to those of Cl in
reactions (1) and (2) (hence salinity in Fig. 3). A rather ambiguous
dependence of leaching on humic concentration suggests that the
polyelectrolyte may, however, interact with additional components
of the paint matrix, including the particle surface itself and,
therefore, act as a ‘‘chemical foulant’’. Thus, although humics are
able to maintain concentrations of metals in solution above the
solubilities of their inorganic salts (and contribute to pseudo-
saturation), they do not appear to be a net driver for the leaching
process itself.
3.6. Environmental implications
The broad findings of the present study based on an hetero-
geneous assortment of spent antifouling paint fragments are,
qualitatively, consistent with what has been established in rotating
cylinder tests on single, well-defined antifouling formulations.
However, it is important to distinguish the practical and environ-
mental differences of the two experimental approaches. Stand-
ardised tests are designed to simulate biocide leaching from the
hull of a moving boat. Because relatively large volumes of artificial
seawater (several L) and low surface areas of paint (a few hundred
cm2) are involved and measurements are taken following a period
of immersion in clean seawater, metal concentrations do not (or
should not) approach pseudo-saturation. The results of our short-
term batch experiments, however, are more applicable to confined,
poorly flushed conditions, the very locations where spent paint
fragments typically accumulate and erode (Page et al., 1996). Thus,
in inter-tidal and sub-tidal sediment deposits in the vicinity of
boating activities, metals may progressively leach into organic-rich
interstitial waters. During disturbance or dredging of the bed
sediment that is contaminated by boat paint, leaching into the
overlying water column is constrained by shorter timescales but,
given the spikes in Cu concentration observed in many experi-
ments (Fig. 2), this could amount to considerable aqueous
concentrations.
The findings of this study have important implications regarding
when and where paint particles are deliberately or inadvertently
disposed of. Specifically, conditions that favour the dissolution of
Cu from paint particles are elevated salinity and, in saline waters,
low temperatures; with regard to Zn, dissolution is favoured by the
opposite conditions. It is uncertain what percentage of leached
metal is bioavailable or toxic (as the free ion or organometallics)
and how rapidly these species adsorb to surrounding sediment.
Nevertheless, it is clear that, directly or indirectly, spent paint
particles represent a significant, localised source of metallic
contamination in aquatic environments impacted by boating
activities.
1.5
1.0
0.5
0.0
0 2 4 6
[HA], mg L-1
376 N. Singh, A. Turner / Environmental Pollution 157 (2009) 371–376
4. Conclusions
Copper and Zn are readily leached from particles of spent anti-
fouling paint under a range of environmental conditions. Qualita-
tively, the extents of metal release are largely consistent with the
mechanisms governing release of Cu and Zn from oxidic and
acrylic-based pigments. However, an increase in leaching of Cu and
Zn with a reduction in temperature under certain conditions is
attributed to complex reaction kinetics and the presence of calcium
carbonate in the paint matrix. Clearly, more research is required
into the environmental and biological impacts exerted by paint
fragments in estuarine and coastal environments where boating
activities are significant.
Acknowledgements
We are grateful to Dr. Andy Fisher for assistance with sample
analysis. NS was supported by an Erasmus Mundus studentship to
undertake a Joint European Masters in Water and Coastal
Management. This study was funded, in part, by the Green Blue
initiative of the Royal Yachting Association/British Marine
Federation.
References
Fay, F., Linossier, I., Langlois, V., Haras, D., Vallee-Rehel, K., 2005. SEM and EDX
analysis: two powerful techniques for the study of antifouling paints. Progress
in Organic Coating 54, 216–223.
Finnie, A.A., 2006. Improved estimates of environmental copper release rates from
antifouling products. Biofouling 22, 279–291.
Hatano, A., Shoji, R., 2008. Toxicity of copper and cadmium in combinations to
duckweed analyzed by the biotic ligand model. Environmental Toxicology 23,
372–378.
Haynes, D., Loong, D., 2002. Antifoulant (butyltin and copper) concentrations in
sediments from the Great Barrier Reef World Heritage Area, Australia. Envi-
ronmental Pollution 120, 391–396.
Howell, D., Behrends, B., 2006. A methodology for evaluating biocide release rate,
surface roughness and leach layer formation in a TBT-free, self-polishing anti-
fouling formulation. Biofouling 22, 303–315.
Kiil, S., Weinell, C.E., Pedersen, M.S., Dam-Johansen, K., 2002. Mathematical
modelling of a self-polishing antifouling paint exposed to seawater: a param-
eter study. Chemical Engineering Research and Design 80, 45–52.
Kogut, M.B., Voelker, B.M., 2001. Strong copper-binding behavior of terrestrial
humic substances in seawater. Environmental Science and Technology 35,
1149–1156.
Leal, M.F.C., van den Berg, C.M.G., 1998. Evidence for strong copper(I) complexation
by organic ligands in seawater. Aquatic Geochemistry 4, 49–75.
Meyer, J.S., Boese, C.J., Morris, J.M., 2007. Use of the biotic ligand model to predict
pulse-exposure toxicity of copper to fathead minnows (Pimephales promelas).
Aquatic toxicology 84, 268–278.
Negri, A.P., Hales, L.T., Battershill, C., Wolff, C., Webster, N.S., 2004. TBT contami-
nation identified in Antarctic marine sediments. Marine Pollution Bulletin 48,
1142–1144.
Omae, I., 2003. Organotin antifouling paints and their derivatives. Applied Organ-
ometallic Chemistry 17, 81–105.
Page, D.S., Ozbal, C.C., Lanphear, M.E., 1996. Concentration of butyltin species in
sediments associated with shipyard activity. Environmental Pollution 91,
237–243.
Sandberg, J., Wallinder, I.O., Leygraf, C., Virta, M., 2007. Release and chemical
speciation of copper from anti-fouling paints with different active copper
compounds in artificial seawater. Materials and Corrosion 58, 165–172.
Schratzberger, M., Wall, C.M., Reynolds, W.J., Reed, J., Waldock, M.J., 2002. Effects of
paint-derived tributyltin on structure of estuarine nematode assemblages in
experimental conditions. Journal of Experimental Marine Biology and Ecology
272, 217–235.
Singh, N., Turner, A. Trace metals in antifouling paint particles and their hetero-
geneous contamination of coastal sediments. Marine Pollution Bulletin, in
press.
Thomas, K.V., Blake, S.J., Waldock, M.J., 2000. Antifouling booster biocide contam-
ination in UK marine sediments. Marine Pollution Bulletin 40, 739–745.
Tolhurst, L.E., Barry, J., Dyer, R.A., Thomas, K.V., 2007. The effect of resuspending
sediment contaminated with antifouling paint particles containing Irgarol 1051
on the marine macrophyte Ulva intestinalis. Chemosphere 68, 1519–1524.
Turner, A., Crussell, M., Millward, G.E., Cobelo-Garcia, A., Fisher, A.S., 2006.
Adsorption kinetics of platinum group elements in river water. Environmental
Science and Technology 40, 1524–1531.
Turner, A., Fitzer, S., Glegg, G.A., 2008. Impacts of boat paint chips on the distri-
bution and availability of copper in an English ria. Environmental Pollution 151,
176–181.
Valkirs, A.O., Seligman, P.F., Haslbeck, E., Caso, J.S., 2003. Measurement of copper
release rates from antifouling paint under laboratory and in situ conditions:
implications for loading estimation to marine water bodies. Marine Pollution
Bulletin 46, 763–779.
Voulvoulis, N., Scrimshaw, M.D., Lester, J.N., 1999. Alternative antifouling biocides.
Applied Organometallic Chemistry 13, 135–143.
Woods Hole Oceanographic Institute, 1952. Marine Fouling and its Prevention. US
Naval Institute, Annapolis, Maryland.
Xue, H.-B., Oestreich, A., Kistler, D., Sigg, L., 1996. Free cupric ion concentrations and
Cu complexation in selected Swiss lakes and rivers. Aquatic Sciences 58, 69–87.
Yebra, D.M., Kiil, S., Dam-Johansen, K., 2004. Antifouling technology – past, present
and future steps towards efficient and environmentally friendly antifouling
coatings. Progress in Organic Coatings 50, 75–104.
Yebra, D., Kiil, S., Dam-Johansen, K., Weinell, C., 2005. Reaction rate estimation of
controlled-release antifouling paint binders: Rosin-based systems. Progress in
Organic Coatings 53, 256–275.
Yebra, D.M., Kiil, S., Weinell, C.E., Dam-Johansen, K., 2007. Dissolution rate
measurements of sea water soluble pigments for antifouling paints: ZnO.
Progress in Organic Coatings 56, 327–337.