Content uploaded by Britta Eklund
Author content
All content in this area was uploaded by Britta Eklund on Sep 08, 2015
Content may be subject to copyright.
1 23
Journal of Soils and Sediments
ISSN 1439-0108
Volume 14
Number 5
J Soils Sediments (2014) 14:955-967
DOI 10.1007/s11368-013-0828-6
Contamination of a boatyard for
maintenance of pleasure boats
Britta Eklund, Lisen Johansson & Erik
Ytreberg
1 23
Your article is published under the Creative
Commons Attribution license which allows
users to read, copy, distribute and make
derivative works, as long as the author of
the original work is cited. You may self-
archive this article on your own website, an
institutional repository or funder’s repository
and make it publicly available immediately.
SOILS, SEC 3 •REMEDIATION AND MANAGEMENT OF CONTAMINATED OR DEGRADED LANDS •RESEARCH ARTICLE
Contamination of a boatyard for maintenance
of pleasure boats
Britta Eklund &Lisen Johansson &Erik Ytreberg
Received: 10 July 2013 /Accepted: 8 December 2013 /Published online: 28 January 2014
#The Author(s) 2014. This article is published with open access at Springerlink.com
Abstract
Purpose The object of this study was to study a boat mainte-
nance facility by investigating the degree of contamination
and assessing how leachate water from soil affects organisms
from three trophic levels.
Materials and methods Surface and subsurface (20-cmdepth)
soil samples were collected in a typical boatyard (200 boats,
12,000 m
2
) at a 70- (station A), 90- (station B), 120- (station C)
and 160-m (station D) distance from the shoreline. Three
replicate samples, ∼10 m apart, were taken at stations A, B
and C, respectively, and one replicate was taken at station D
(i.e. altogether 20 samples with 10 at surface and subsurface,
respectively). The total copper (Cu), lead (Pb), tin (Sn) and
zinc (Zn) concentrations were determined for all replicates.
Pooled samples from the respective stations were used for
analysis of organotin compounds, irgarol and polyaromatic
hydrocarbons. Leachate waters were produced from the pooled
samples and used for toxicity testing with the bacterium Vi brio
fischeri, the macroalga Ceramium tenuicorne and the crusta-
cean Nitocra spinipes.
Results and discussion Very high concentrations of Cu, Pb,
Zn were detected, with maximum values of 16,300, 6,430 and
18,600 mg/kg dw, respectively. Organic hazardous com-
pounds were found in high concentrations with maximum
values of 37, 27 and 16 mg/kg dw for tributytin (TBT),
dibutyltin (DBT) and triphenyltin (TPhT), respectively. All
pollutants exceeded existing guidance values for both
sensitive land use and less sensitive land use by several
factors, in both surface and subsurface soil. The least and
worst cases of total amount of TBT (12 000 m
2
and 0.2 m
depth) were estimated to be 10 and 122 kg of TBT. Leachates
were shown to be toxic in all three test organisms.
Conclusions Several known hazardous pollutants were found
in boatyard maintenance areas and they exceeded recom-
mended guidance values by several factors. Leachates were
shown to be toxic to test organisms of several trophic orders.
This underlines that boat maintenance facilities in general
should be better regulated to minimize further exposure to
humans and spread of contaminants in the environment. The
amounts of contaminants accumulated in these areas call for
investigations of how remediation should be performed.
Keywords Antifouling paint .Boatyard .Contaminants .
Tributyltin (TBT)
1 Introduction
Maritime transporters have battled marine biofouling, a natu-
ral process of undesirable attachment and accumulation of
microorganisms, plants and animals on underwater surfaces,
for the last 3,000 years (e.g. Lunn 1974; Almeida et al. 2007).
The adverse effects of biofouling are well known, including
higher frictional resistance, which results in increased fuel
consumption and hull maintenance costs (Abarzua and
Jakubowski 1995). Currently, the most common strategy for
preventing biofouling is to coat the boat hull with antifouling
paints containing various biocidal substances. During the
1970s and 1980s, organotin (e.g. tributyltin, TBT) formula-
tions were the most frequently used biocide added in antifoul-
ing paints (Fent 2006). However, due to adverse effects on
marine biota (Alzieu et al. 1986; Alzieu 1991;Champ2000),
in the late 1980s, several countries restricted the use of these
Responsible editor: Jianming Xu
B. Eklund (*):L. Johansson
Department of Applied Environmental Science (ITM), Stockholm
University, 10691 Stockholm, Sweden
e-mail: britta.eklund@itm.su.se
E. Ytreberg
Department of Shipping and Marine Technology, Chalmers
University of Technology, 41296 Göteborg, Sweden
J Soils Sediments (2014) 14:955–967
DOI 10.1007/s11368-013-0828-6
formulations to leisure crafts (e.g. Alzieu 1991;EUDirective
89/677/EEC 1989). Since 2008, there has been a global ban of
TBT for all sizes of ships due to the adoption of the AFS
convention by the International Maritime Organization (IMO
2001). Albeit, the phasing out of TBT-based antifouling paints
and of TBT and its degradation products, dibutyltin (DBT)
and monobutyltin (MBT), is still observed in high concentra-
tions in sediments at marinas, harbours and estuaries (Eklund
et al. 2008). Today, copper (e.g. cuprous oxide) has replaced
TBT as the main biocide on the market (Jones and Bolam
2007). For example, in Sweden, all biocide-leaching antifoul-
ing paints which are approved to be used on leisure boats
contain copper as active substance (The Swedish Chemical
Agency, www.kemi.se). Zinc is also a common ingredient
added to paint formulations, serving as a binder/pigment
(Yebra et al. 2004 and references therein; Singh and Turner
2009 and references therein). Due to the widespread use of
antifouling paints, elevated concentrations of both copper and
zinc have been observed worldwide in areas with high boat
activity, such as marinas (Turner 2010;KylinandHaglund
2010), harbours (Eklund et al. 2010), estuaries (Matthiessen
et al. 1999) and ship lanes (Strand et al. 2003).
There is a growing body of research on release rates, fate
and effects of TBT, copper and zinc leached from antifouling
paints (Finnie 2006; Yebra et al. 2006; Karlsson et al. 2010;
Ytreberg et al. 2010). The bio-accessibility of paint particles
found in sediment and the effects on different organisms have
been investigated (Turner et al. 2009a,b,c). Recently, a
review was done of the marine pollution from antifouling
paint particles (Turner 2010). What is studied less is how
scraped off antifouling paint at boatyards ends up in the
ground and how it affects biota.
The aim of this study was to do an environmental
risk assessment of a Swedish boatyard. This was achieved by
determining the extent of soil contamination and by producing
leachate water from the soil, which was used in ecotoxicological
assays.
2 Material and methods
2.1 Sampling area
The boatyard studied is located in Stockholm inner archipel-
ago and has an area of approximately 12,000 m
2
. Since 1955,
the facility has been used for winter storage for approximately
200 leisure boats.
2.2 Sampling
The soil from the boatyard was sampled in June2010, after the
launching of boats. Four station levels were chosen for the
sampling, based on their distance from the shore: stations A,
B, C and D, were, respectively70, 90, 120 and 160 m from the
shore. At stations A, B and C, three replicates of soil sample,
approximately 10 m apart from each other, were collected to
determine the variation of the contamination. At station D,
only one replicate was sampled. The soil samples were col-
lected by digging with a spade, and at each location, both
surface (0–0.5 cm) and subsurface (19–21 cm) samples were
collected. Thus, the total number of samples was 20. All
samples were filtered through a 3-mm mesh to remove larger
stones. Dry weight (dw), total organic carbon (TOC) and loss
on ignition (LOI) and the concentration of copper (Cu), lead
(Pb), tin (Sn) and zinc (Zn) were measured on all samples.
Analyses of tin organic substances, irgarol and polyaromatic
hydrocarbons (PAHs) were done on pooled samples of the
respective replicates from stations A to C and from station D.
All measured substances, except PAHs, have been or are still
used as active ingredient in antifouling paints.
2.3 Leachate production
In the leaching experiment, soil (300 g) and Milli-Q water
(500 mL) were added to pre-cleaned glass beakers. The sub-
samples from sites A to C were pooled (i.e. 100-g soil from the
three respective replicates was added to the beakers). This
procedure was conducted for both surface and subsurface soil
samples. After 24 h of incubation, with constant shaking, the
soil particles were left to precipitate for an additional 72 h. The
water phase was filtered through a 0.45-μm filter for dissolved
metal analysis of the most commonly used metals in antifoul-
ing paints, i.e. Cu, Zn and Pb, and stored refrigerated (4 °C)
before being used in ecotoxicological tests.
2.4 Chemical analyses
2.4.1 Chemical analysis of soil samples
For all soil samples, analysis of dw, TOC and LOI was
performed according to standardized procedures (SS
028113-1). Metal (Cu, Pb, Sn and Zn) analyses were carried
out with ICP-MS (SS-EN-ISO 17294-2) after extraction of the
soil in nitric acid (SS 028150). Analyses of organic tin com-
pounds (monobutyltin (MBT), dibutyltin (DBT), tributytin
(TBT), monophenyltin (MPT), biphenyltin (DPT),
triphenyltin (TPT)), polyaromatic hydrocarbons (PAH) and
irgarol were performed by the laboratory ALS Scandinavia
AB, which is accredited for all analysis except irgarol. The
soil was extracted with MeOH/hexane and, after cleaning and
derivatization, the tin organic compounds were determined by
GC-FPD (DIN EN ISO 17253). For measurement of PAHs,
the soils were extracted with acetone-hexane-cyclohexane
(1:2:2) and the 16 most common forms of PAHs were
analysed with GC-MS, based on the standard CSN EN ISO
11396. Irgarol was also determined with GC-MS.
956 J Soils Sediments (2014) 14:955–967
2.4.2 Chemical analysis of leachate water
All dissolved metal analyses were performed by an accredited
laboratory at our department (Department of Applied
Environmental Science (ITM), Stockholm University).
Water samples were preserved by acidification with HNO
3
(final concentration 0.2%) and analysed for total dissolved
(<0.45 μm) concentrations of Cu, Pb and Zn by inductively
coupled plasma mass spectrometry (ICP-MS) using a Thermo
X series II from Thermo Fisher (Bremen, Germany). The
method detection limits for Cu, Zn and Pb were 0.2, 1.0 and
0.05 μg/L, respectively.
2.5 Biological tests on leachate waters
Since run-off from the boatyard ends up in the Baltic Sea,
brackish water test organisms were used. Three organisms
were used: the bacterium Vibrio fischeri, the red macroalga
Ceramium tenuicorne and the harpacticoid copepod Nitocra
spinipes. The latter two are common in the Baltic Sea and in
marine waters.
2.5.1 Microtox® light inhibition test
The Microtox® toxicity tests were performed using the biolu-
minescent bacterium V. fischeri according to the Basic Test
procedure described in ISO 11348-3 (ISO 2007). The
Microtox® toxicity test measures the concentration (percent
leachate) that causes a 50% reduction of bioluminescence
(EC50) from the bacterium. The bacterium and all solutions
(i.e. reconstituent solution, diluents and osmotic adjustment
solution) used in the test were obtained from Strategic Diag-
nostics Inc. (SDI, Newark, NJ, USA). Two replicates were used
at each concentration and the test solutions were diluted in
Milli-Q water and adjusted to salinity 20‰using osmotic
adjustment solution. For each test, nine concentrations were
tested; they ranged from 0.3 to 81.9% leachate water (each
treatment increasing by a factor of 2). Ten-microliter bacteria
wereaddedtoeachsampleandthebioluminescencewasmea-
sured in a photomultiplier before exposure to the leachate water
and after an incubation time of 15 min. The test medium and the
bacterium were kept at 15± 1 °C during the whole procedure.
2.5.2 Ceramium growth inhibition test
The C. tenuicorne growth inhibition test was performed
according to the procedure described in Eklund (2004)
and ISO 2010. The stock leachate water was adjusted to
7 PSU with NaCl and enriched with nitrogen (3.46 mg/L),
phosphorus (0.78 mg/L) and iron (0.10 mg/L). Dilution series
were made of the leachate water by dilution with filtered
(30 mm) autoclaved enriched (N 3.46 mg/L, P 0.78 mg/L
and Fe 0.10 mg/L) natural seawater of 7 PSU. This nutrient-
enriched natural seawater was also used as control. In the test,
the top pieces (2–3 mm in length) of the alga were exposed to
leachate dilutions for 1 week. The length of the algae was
measured at the start and at the end of the test. The algal
growth rates in the different test solutions were calculated and
compared with that of a control, whereupon EC50 values were
calculated. All tests were performed in sterile polystyrene
Petri dishes, in four replicates for each test treatment with
two pieces of algae added to each dish. During exposure, the
dishes were kept at 22±2 °C, a light regime of 10 h darkness
and 14 h light at a light intensity of 70±7 μmol m
−2
s
−1
.
2.5.3 Nitocra larval development test (LDR)
The LDR is a partial life cycle test based on the method
described in Breitholtz and Bengtsson (2001), which mea-
sures larval development ratio (LDR) and mortality. The
naupliar (larval) and copepodite (juvenile) stages are morpho-
logically distinct in copepods and are therefore easily ob-
served. LDR is recorded after 5 to7 days when ∼50% of the
control animals have reached the copepodite stage and is
expressed as the percentage of copepodites among all living
copepods at the end of the test. The salinity of the stock
leachate water was increased to 6.5 PSU by addition of NaCl.
Natural filtered seawater from an uncontaminated site was
used as control and dilution media for the test concentrations.
This water was, prior to use, filtered (0.03-mm paper filter)
and heated to 80 °C and then GF/C-filtered (1.2-μmglass
microfibre filter) to eliminate larger particles and organisms.
At start of each test, ten nauplii (<24 h old) were randomly
transferred to the test vials; eight replicates per treatment and
control were used. The test vials were incubated in a climate
chamber in darkness at 22±2 °C throughout the experiment.
The crustaceans were fed with Rhodomonas salina (final
density of 5×10
7
cells mL
−1
) at the start as well as after days
2 and 5 when 70% of the test medium was changed. Evapo-
ration losses were compensated for by adding distilled water
each time the test medium was changed. The temperature, pH
and dissolved oxygen were measured on days 0, 2 and 5 and at
the end of the experiment.
2.6 Statistical analysis
EC50 calculations of the Microtox luminiscens inhibition test
with the bacteria V. fischeriwere performed using the software
MicrotoxOmni 1.8. For calculation of EC values for the
Ceramium growth inhibition test, the software RegTox ver
6.4 was used (http://eric.vindimian.9online.fr). For the
crustacean assay, LDR and mortality were calculated using
one-tailed Fisher’s exact test and the non-parametric Kruskal–
Wallis ranking test, followed by a one-sided Mann–Whitney
comparison to check for differences between the treatments
and the control. Bonferroni corrections were made to correct
J Soils Sediments (2014) 14:955–967 957
for compounded alpha error for multiple comparison against
the same control (i.e. differences were deemed significant at
the 0.05 level if the p-value was ≤0.01) equals five compari-
sons against the same control.
3Results
3.1 Chemical concentrations in soil and soil leachates
3.1.1 Chemical concentrations of soil samples
The characteristics of thesoil are presented in Table 1. The soil
consisted of gravel, which is reflected by the low TOC and
LOI at all samples from stations A, B and C. At station D,
which was farthest from the shore, a higher TOC and LOI
were observed, especially in the surface sample.
Table 2presents the metal (Cu, Pb, Zn, Sn) composition of
surface and subsurface soil samples. The values higher than
the Swedish guidance values for less sensitive land use (LSL)
are shown in red/dark grey and values higher than those for
sensitive land use (SL) (i.e. residential areas) are shown as
yellow/light grey. Guidance values exist for Cu, Pb and Zn
and are for SL 80, 50 and 250 mg/kg dw, respectively, and for
LSL 200, 400 and 500 mg/kg dw. The Cu LSL value was
exceeded in 19 of the copper samples and in the remaining
sample, it was higher than the guidance value for SL. For Pb 8,
all of the ten samples from the surface and subsurface, respec-
tively, were higher than the SL guidance value and six and
seven out of ten samples from surface and subsurface, respec-
tively, were higher than LSL. The corresponding figures for
Zn were as follows: eight and nine of the samples from surface
and subsurface, respectively, were higher than the SL guid-
ance value and half of the surface samples and seven of the
subsurface exceeded the LSL guidance value. The highest
concentration of Cu (16,300 mg/kg dw) and Zn (18,600 mg/kg
dw) was found in the surface soil, which exceeded the guid-
ance value for SL by a factor of 204 (Cu) and 74 (Zn). For Pb,
the highest concentration was found in a subsurface sample
(6,340 mg/kg dw), which exceeded the guidance value for SL
byafactorof129.
A very high variation in metal (Cu, Pb, Sn, Zn) concentra-
tions was observed among the replicate soil samples at each
station (Table 2). Despite the variation, the surface samples at
stations A, B and C contained a significant lower concentra-
tion of Cu and Sn as opposed to the subsurface samples
(Mann–Whitney nonparametric test; Cu p=0.014, Pb p=
0.067, Zn p=0.206, Sn p=0.017). In contrast, at station D, a
notable higher metal concentration was observed in the sur-
face sample as compared to the subsurface sample, for Cu, Pb
and Zn and similar concentrations for Pb.
The concentrations of six tin organic contaminants
(monobutyltin (MBT), dibutyltin (DBT), tributytin (TBT),
monophenyltin (MPhT), diphenyltin (DPhT) and triphenyltin
(TPhT)) are shown in Table 3. There are no Swedish guidance
values for these substances in soil, but in Finland, the corre-
sponding value for SL and LSL is for the sum of TBT+TPhT
1,000 and 2,000 μg/kg dw, respectively (Finnish Directive
2007). In comparison to these, all subsurface samples and
three of the four surface samples exceeded LSL. The highest
(TBT+TPhT) concentration was measuredin the surface sam-
ple from station D (53,000 μg/kg dw) and exceeded the
Finnish guidance value for SL and LSL by a factor of 53
and 26, respectively.
For all stations, the proportion of the most toxic organotin
compounds (i.e. TBT, DBT and TPhT) as compared to total
Sn was found to be lower in the surface soil compared to the
subsurface soil (Table 3).
Tabl e 1 Characteristics of
surface (0–0.5 cm) and subsurface
(20 cm) soils at a boatyard located
in Stockholm archipelago.
Swedish guidance values for
contaminated soil exist for copper
(Cu), zinc (Zn) and lead (Pb) and
differentiated between SL
(sensitive land use) and LSL
(less sensitive land use)
Location Surface soil (0–0.5 cm) Subsurface soil (19–21 cm)
dw % LOI % TOC % dw % LOI % TOC %
70 m from the water, A1 99.1 1.4 0.8 97.0 1.8 1.0
70 m from the water, A2 99.3 1.5 0.9 95.3 2.4 1.4
70 m from the water, A3 99.8 1.2 0.7 95.6 1.7 1.0
Mean±sd 99.4±0.36 1.4±0.15 0.8±0.1 96.0±0.91 2.0±0.38 1.1±0.23
90 m from the water, B1 99.3 1.7 1.0 97.8 1.7 1.0
90 m from the water, B2 99.6 1.0 0.6 98.0 1.7 1.0
90 m from the water, B3 99.8 1.2 0.7 96.5 1.6 0.9
Mean±sd 99.6±0.25 1.3±0.36 0.77±0.21 97.4±0.81 1.7± 0.06 0.97± 0.06
120 m from the water, C1 99.6 2.1 1.2 98.5 2 1.1
120 m from the water, C2 99.8 1.3 0.7 98.8 1.5 0.9
120 m from the water, C3 99.8 0.9 0.5 98.5 0.9 0.5
Mean±sd 99.7±0.12 1.4±0.61 0.8±0.36 98.6± 0.7 1.5±0.55 0.83±0.31
160 m from the water, D 97.2 13.9 7.9 93.2 7.2 4.1
958 J Soils Sediments (2014) 14:955–967
For the remaining analysed organotin compounds,
monooctyltin, dioctyltin and tricyclohexyltin were all be-
low the detection limit 50 μg/kg dw. Tetrabutyltin was
foundonlyatstationDinthesurfaceandsubsurfaceat
71 and 58 μg/kg dw.
The concentrations of irgarol and PAHs and carcinogenic
PAHs are presented in Table 4. There are no Swedish guidance
values to compare the irgarol value with. The concentrations
of both the carcinogenic and the total (∑16 PAH) were below
the Swedish guidance values for soil for all analysed samples.
Table 2 Characteristics of surface (0–0.5 cm) and subsurface (19–
21 cm) soils at a boatyard located in Stockholm archipelago. Three
replicates for samples A, B and C and one for sample D. Swedish
guidance values for contaminated soil exist for copper (Cu), zinc (Zn)
and lead (Pb) and differentiated between SL (sensitive land use) and LSL
(less sensitive land use). No guidance value exists for Sn
Surface soil
(0–0.5 cm)
Subsurface soil
(19-21 cm)
Location
Cu
mg/kg
dw
Pb
mg/kg
dw
Zn
mg/kg
dw
Sn
mg/kg
dw
Cu
mg/kg
dw
Pb
mg/kg
dw
Zn
mg/kg
dw
Sn
mg/kg
dw
70 m from the water, A1 205 33 181 < 1 479 336 288 20.7
70 m from the water, A2 315 289 343 3.8 1 400 5 360 975 38.4
70 m from the water, A3 423 167 874 6.9 214 170 232 8.7
Mean ± sd 314
± 109
163
± 128
466
±363
5.4
± 2.2
698
± 623
1 955
± 2950
498
± 414
22.6
± 15
90 m from the water, B1 461 2230 427 18.8 1840 6 430 1 290 51.4
90 m from the water, B2 140 45 155 < 1 1430 1 490 1 570 27.8
90 m from the water, B3 368 441 1 350 11.1 1010 1 110 1 190 21.4
Mean ± sd 323
± 165
905
± 1164
644
± 626
15
± 5.4
1 427
± 415
3 010
± 2968
1 350
± 197
33.5
± 15.8
120 m from the water, C1 1 600 1 600 1 900 49.3 1 900 2 280 2 040 61.7
120 m from the water, C2 754 890 668 25.2 1 190 976 887 25.7
120 m from the water, C3 349 476 450 12.2 388 276 389 5.4
Mean ± sd 901
± 638
989
± 569
1 006
± 782
28.9
± 18.8
1159
± 757
1 177
± 1 017
1 105
± 847
30.9
± 28.5
160 m from the water, D 16 300 1 640 18 600 554 3 970 1 630 1 410 259
Values higher than SL are marked yellow/light grey and higher than LSL are marked red/dark grey
Table 3 Concentrations of tin organic contaminants in comparison to
inorganic tin (Sn) in a boatyard in the Stockholm archipelago. The analyses
are performed on pooled samples from three replicates for A, B and C and for
D on one sample (MBT= monobutyltin, DBT=dibutyltin, TBT= tributyltin,
MPhT= monophenyltin, DPhT=diphenyltin, TPhT=triphenyltin). The ratio
of organic Sn in percent of inorganic Sn is based on the Sn content of the
three most toxic compounds: DBT, TBT and TPT
MBT
(mg/kg dw)
DBT
(mg/kg dw)
TBT
(mg/kg dw)
MPhT
(mg/kg dw)
DPhT
(mg/kg dw)
TPhT
(mg/kg dw)
Organic Sn in %
of inorganic Sn
Concentrations in surface soil (0–0.5 cm)
70 m from the water, A 1.1 0.79 0.85 0.63 <0.050 0.48 17
90 m from the water, B 1.4 1.2 2 0.91 <0.050 0.26 10
120 m from the water, C 4.5 4.7 8 0.73 <0.050 0.43 20
160 m from the water, D 6.5 27 37 1.9 0.190 16 6
Concentrations in subsurface soil (19–21 cm)
70 m from the water, A 4.4 5 6.2 1 <0.050 0.063 23
90 m from the water, B 5.4 4.1 5.9 0.61 <0.050 0.190 29
120 m from the water, C 5.7 4.7 6.1 0.89 <0.050 0.320 18
160 m from the water, D 1 27 31 0.73 <0.050 1.3 10
J Soils Sediments (2014) 14:955–967 959
3.1.2 Total amount of contaminants in the soil
The least bad and the worst cases of the total amount of
contaminants in the boatyard are shown in Table 5. The area
is estimated to be 12,000 m
2
and the depth ofcontamination is
assumed to 0.2 m. This equals 2,400 m
3
of contaminated soil.
With the assumption that 1 L soil corresponds to 1.5 kg soil,
we have calculated least bad and worst case scenarios of the
amounts of contaminants at this boatyard. The measured
concentrations in the surface and the subsurface values were
used to calculate a mean value. The lowest and the highest
values of all the mean values have been used to illustrate the
least bad and worst case scenarios.
Calculation of least and worst cases was performed as
follows:
Mean of all analysed element/compound at each of the A,
B, C and D location (Cu, Pb, Zn, Sn= six samples per location
A, B and C and two from D, organotin and polyaromatic
carbons=two samples/location, irgarol two samples at in all
two locations) was calculated. Calculation of median contam-
ination was based on the median values of all analysed sam-
ples (See Tables 2,3and 4) which were multiplied with the
area (12,000 m
2
and depth (0.2 m).
The least bad and the worst case means for Cu are 1.8 and
36.5, Pb 3.8 and 6.9, Zn 1.7 and 36 t, respectively. For the
most toxic organotin compounds, the total amount for TBT is
10 and 18 and for TPhT 3 and 5 kg.
3.1.3 Chemical concentrations—leachate waters
The leachate water was analysed with respect to metal (Cu, Pb
and Zn) concentrations and is presented in Table 6.Hence,no
leachate data are available for tin organic compounds, PAHs
and irgarol concentrations. As opposed to the metal concen-
trations in soil samples, the concentrations of metals were
generally higher in the surface leachates as compared to the
subsurface leachates.
3.2 Toxicity of leachate water
The effect of leachate water on V. fischeri,C. tenuicorne and
N. spinipes in presented in Tables 7,8and 9. The macroalga
C. tenuicorne was the most sensitive species tested, followed
by the crustacean N. spinipes; the bacteria V. fischeri were the
least sensitive species. Cu and Zn have been found to cause a
50% reduction in bioluminescence for the bacterium
V. fischeri, at 800 μg Cu/L and 2,000 μg Zn/L (Ytreberg
et al. 2010). For the macroalga C. tenuicorne, EC50 values
of 4.9–8.0 μgCu/Land21–30 μgZn/Lhavebeenreported
(Eklund 2005, Ytreberg et al. 2010). For the crustacean
Tabl e 4 Concentrations of or-
ganic contaminants in a boatyard
in the Stockholm archipelago
The analyses are performed on
pooled samples from three repli-
cates for A, B and C and for D on
onesample(Σ16 PAH=total
concentration of 16 compounds
analysed according to EPA. PAH
carc. shows the concentration of
the carcinogenic PAHs). na= not
analysed
Location Irgarol
(mg/kg dw)
PAH Σ16 EPA
(mg/kg dw)
PAH c arc.
(mg/kg dw)
Concentrations in surface soil (0–0.5 cm)
70 m from the water, A 0.063 1.3 0.41
90 m from the water, B na 1.3 0.22
120 m from the water, C na 5.7 3.1
160 m from the water, D 54 9.4 5.4
Concentrations in subsurface soil (19–21 cm)
70 m from the water, A 1.8 3.6 2.0
90 m from the water, B na 1.8 1.1
120 m from the water, C na 7.0 3.9
160 m from the water, D 0.87 2.6 1.8
Tabl e 5 The total amount of elements/compounds at the investigated
boatyard
Element/compound Median Least Worst
(kg) (kg) (kg)
Cu 2,200 1,800 36,500
Pb 3,400 3,800 6,900
Zn 3,200 1,700 36,000
Sn 76 48 1,500
MBT 22 13 120
DBT 17 10 97
TBT 16 10 122
MPhT 2 1 31
TPhT 3 3 5
Irgarol 5 3 99
PAH Σ16 EPA 11 6 23
PAH ca r c. 7 2 1 3
The area is 12,000 m
2
and the depth of contamination is assumed to be
0.2 m. The mean ofsurface and subsurface values has been calculated and
the lowest and highest values have been used to show the least and worst
scenarios. The median value is based on all analyses of each element/
compound. The assumption is that 1 L soil=1.5 kg soil. No values are
given for DPhT because of concentrations below detection level
960 J Soils Sediments (2014) 14:955–967
N. spinipes, both Cu and Zn have been reported to have
significant effects on LDR at 110 μgCu/L(NOEC=
49 μg/L) and 400 μg Zn/L (NOEC=190 μg/L) (Ytreberg
et al. 2010). These reported LOEC/EC50 values were subse-
quently used to determine if Cu and/or Zn in the leachate
dilutions could be responsible for the observed toxic response
or if other non-analysed contaminants may have contributed
as well.
3.2.1 Microtox® light inhibition test to Vibrio fischeri
Only two leachates caused a measurable toxic response onthe
bacterium V. fischeri(i.e. D surface (EC50= 16% leachate) and
D subsurface (EC50= 41% leachate)) (Table 7). However,
the bacterium was also affected by surface leachate waters
from stations A and C with extrapolated EC50 of 165 and
180%, respectively. Based on the toxic responses to single
substances, the concentration of Zn in these leachate dilutions
may explain the toxicity.
3.2.2 Growth inhibition test to Ceramium tenuicorne
All leachates were toxic to C. tenuicorne (Table 8). Of the
leachates tested, those from station D were most toxic to the
macroalga and as little as 0.25 and 0.31% leachates were
enough to cause a 50% reduction in growth rate when the
algae were exposed to surface and subsurface leachate, re-
spectively. Surface leachates from stations A and B displayed
high toxicity, EC50=1.35 and 1.72% leachates, respectively.
The Zn concentrations in the leakage water from the surface
samples can partly explain the observed toxicity in surface
samples, but it cannot for the subsurface samples. In station C,
the copper concentration may also be contributing to the
toxicity.
Table 6 Concentrations of copper (Cu), lead (Pb) and zinc (Zn) in
surface and subsurface leachate waters
Location Cu (μg/L) Pb (μg/L) Zn (μg/L)
Surface leachate (0–0.5 cm)
70 m from the water, A 61 2 2,117
90 m from the water, B 40 3 1,208
120 m from the water, C 117 14 583
160 m from the water, D 809 17 13,910
Subsurface leachate (19–21 cm)
70 m from the water, A 31 2 94
90 m from the water, B 33 21 32
120 m from the water, C 43 10 172
160 m from the water, D 458 28 5,076
The analyses are performed on pooled samples from three replicates for
A, B and C and for D on one sample
Tabl e 7 Luminescence inhibition test with Vib rio fisc heri exposed to
leachate water from soil samples from a boatyard
Sample Estimated conc.
Leachate Cu Zn
(%) (μg/L) (μg/L)
Surface leachate (0–0.5 cm)
70 m from the water, A 165 101 3,493
90 m from the water, B na
120 m from the water, C 180 211 1,049
160 m from the water, D 16 129 2,225
Subsurface leachate (19–21 cm)
70 m from the water, A na
90 m from the water, B na
120 m from the water, C na
160 m from the water, D 41 187 2,081
The tests were performed on pooled samples from three replicates for A,
B and C and for D on one sample. Corresponding Cu and Zn concentra-
tions are calculated from analysed leachate and bold figures denote
substances most likely to be responsible for the observed toxicity based
on responses to single substances. Observe extrapolation of two points.
EC50 for Vibrio fischeri and Cu and Zn as single substances are 800 and
2,000 μg/L, respectively (Ytreberg et al. 2010). na=not analysed
Tabl e 8 Growth inhibition test with the macroalga Ceramium tenuicorne
exposed to leachates in 7‰natural seawater (NSW)
Sample Estimated conc.
Leachate Confidence
interval
Cu Zn
(%) 95% (μg/L) (μg/L)
Surface leachate (0–0.5 cm)
70 m from the water, A 1.35 (0.6–2.2) 0.83 28.6
90 m from the water, B 1.72 (1.2–2.4) 0.7 20.8
120 m from the water, C 5.52 (4.4–6.8) 6.5 32.2
160 m from the water, D 0.25 (0–1.0) 2.0 34.8
Subsurface leachate (19–21 cm)
70 m from the water, A 16 4.9 15.0
90 m from the water, B 39.7 (30–48) 13.2 12.9
120 m from the water, C 5.14 (3.1–7.2) 2.2 8.8
160 m from the water, D 0.31 (0.27–0.34) 1.4 15.7
The tests were performed on pooled samples from three replicates for A,
B and C and for D on one sample. EC50 values (% added leachate) are
presented with 95% confidence intervals. Corresponding estimated Cu
and Zn concentrations are calculated from analysed 100% leachate. Bold
figures denote substance most likely to be responsible for the observed
toxicity, based on responses to single substances. EC50 for Ceramium
tenuicorne and Cu and Zn as single substances is 4.9–8.0 and 21–
30 μg/L, respectively (Ytreberg et al. 2010)
J Soils Sediments (2014) 14:955–967 961
For the subsurface leachates, Cu could explain the toxic
response at stations A and B. However, at stations C and D,
neither Cu nor Zn could explain the toxic response.
3.2.3 Larval development ratio (LDR) test with Nitocra
spinipes
An acute mortality test on adult crustacean was performed
prior to the LDR test to identify which water had toxic
capacity to influence the development of the crustacean
(unpublished results). These “screening results”sug-
gested that surface leachates A, C and D and subsurface
leachate C may have had an inherent capacity to cause
an adverse effect on larval development, and conse-
quently they were chosen for LDR testing. However,
the LDR test showed that only two waters had an effect
on development, i.e. surface leachates A and D (Table 9). In
both cases, the concentration of Zn may partly be the cause of
the toxicity.
4 Discussion
Altogether, the soil of the boatyard proved to be highly con-
taminated by Cu, Pb, Zn, irgarol and different organotin
contaminants, in both the surface and the subsurface. In most
samples, the Swedish guidance values for contaminated soil
for SL and LSL were exceeded by several factors. For exam-
ple, the SL guidelines for Cu, Pb and Zn were exceeded by up
to 204, 60 and 74 times, respectively. The sum of TBT and
TPhT was up to 53 times higher than the corresponding
Finnish guidance value for SL of 1 mg/kg dw (Finnish
Directive 2007). In addition, in many samples, the higher
guidance values of LSL were exceeded (see Tables 2and 3).
According to the European Chemical Substance Information
System (2008), the hazardousness of these compounds are
classified as “very high”for TBT, DBT, TPhT, PAHs and lead,
“high”for copper and irgarol and “moderate”for zinc. Except
for PAHs, the high concentrations of these compounds dem-
onstrate that this site is highly contaminated.
4.1 Occurrence and amounts of contaminants in boatyards
Only few studies of contaminated boatyards have been found
in the scientific literature. Metal concentrations were deter-
mined in three samples from surface soilof two marine leisure
boatyards in UK (Turner 2013). The concentrations of Cu, Pb,
Zn and Sn at both investigated sites were consistent with our
findings. Similarly, very high levels of contaminants were
shown in an extensive compilation of 34 investigations per-
formed in the last 15 years of boatyards in Swedish coastal
municipalities (Eklund and Eklund 2013). The concentrations
were much lower in the surface compared to the subsurface at
stations A and B and slightly lower at station C (Tables 2and
3). The year before the sampling, a layer of new macadam was
placed on top of the ground at the lower part of the boatyard
(stations A and B). This means there had been less time for
pollutants to accumulate in the surface soil there and might be
the reason for the differences between the studies.
The most polluted place in the boatyard was station D
where all measured contaminants were found in the highest
concentrations in the surface soil. Station D is in the farthest
end of the yard. This is also where boats in need of more
extensive repairs had been placed. Often this involved remov-
al of all paint layers, which explain the high values of all
measured contaminants. Notably, TBT, which has been
prohibited for use on pleasure boats since 1989 (89/677/
EEC), was also found at very high concentrations in the
surface soil. The reason might be that older layers of paint
that contained TBT come off in the maintenance work and
accumulate in the ground. This hypothesis was also suggested
by Eklund et al. (2008,2010).
The reasoning used for with toxic paint layers may apply to
lead paint, which was used on wooden boats. Because of its
harmful properties, use of lead has been restricted since 1976
(Directive 76/769/EEC 1976; EU Directive 89/677/EEC
1989;UN2008). Around 30% of the boats at this boat club
studied are wooden, which explains the very high levels of
lead both in the surface and the subsurface samples compared
to the findings in Eklund and Eklund (2013). In Thailand, lead
still is used extensively in repair work with wooden boats
(Maharachpong et al. 2006). Maharachpong et al. studied lead
Table 9 Larval development ratio (LDR) test with Nitocra spinipes
exposed to leachates in 7‰natural seawater (NSW)
Sample NOEC LOEC Estimated conc.
Leachate
(%)
Leachate
(%)
Cu
(μg/L)
Zn
(μg/L)
Surface leachate (0–0.5 cm)
70 m from the water, A 3 9 5.5 191
90 m from the water, B na na
120 m from the water, C 45 na
160mfromthewater,D2649.0835
Subsurface leachate (19–21 cm)
70 m from the water, A na na
90 m from the water, B na na
120 m from the water, C 18 18
160 m from the water, D na na
The tests were performed on pooled samples from three replicates for A,
B and C and for D on one sample. Corresponding estimated Cu and Zn
concentrations are calculated from analysed 100% leachate. Bold figures
denote substance most likely to be responsible for the observed toxicity,
based on responses to single substances. NOEC for Nitocra spinipesLDR
and Cu and Zn as single substances is 49 and 400 μg/L, respectively
(Ytreberg et al. 2010). na=not analysed
962 J Soils Sediments (2014) 14:955–967
in dust at different distances from a shipyard and found
concentrations between 1 and 7,770 mg Pb/kg dw with the
peak in the central areas, which is similar to the maximum
value of 6,430 mg Pb/kg dw at our boatyard (Table 2).
The variation between samples was high and ranged be-
tween 30 and 150%. This large variation is in accordance with
the variation found in other studies (Maharachpong et al.
(2006), Turner et al. (2013), Eklund and Eklund (2013)).
The reason is the uneven distribution of paint flakes originat-
ing from the scraping of the boats.
The amount of hazardous metals at this boatyard is esti-
mated to totals of several tons Cu, Pb and Zn and the most
toxic organotin compound TBT totals up to 122 kg in the
worst scenario (Table 5). These calculations were made using
the assumptions, i.e. that the contaminated area is 12,000 m
2
,
the soil is contaminated 0.2 m down and 1 L of soil
corresponds to 1.5 kg.
This boatyard may be regarded as typical in size
(12,000 m
2
) and in the number of boats (200). The total
amount based on the median value of Cu, Pb, Zn and TBT
was 2.2, 3.4, 3.2 and 0.016 t, respectively (Table 5), which is a
considerable amount of toxic substances. In different coun-
tries, the habit of using antifouling paints is similar, and
therefore, the figures presented here may be seen as a typical
example for maintenance yards for pleasure boats.
4.2 Toxicity of contaminants found in boatyards
The Cu, Pb, irgarol and the organotin compounds DBT, TBT
and TPTare in the soil because of their use as active agents in
antifouling paints (e.g. Yebra et al. 2004;ThomasandBrooks
2010). Zn is commonly used as a binder in the paint formu-
lation; the high correlation between Cu and Zn (R=0.98) and
Sn and Zn (R=0.92) further confirms the origin for these
elements as being antifouling paints. An overview of the
toxicity of substances used in antifouling paints has recently
been made by Dafforn et al. (2011 and references therein).
Lead was formerly extensively used as an active substance
in red lead paint, which was especially effective for preventing
ship worm in wooden boats (Lunn 1974). It delays the devel-
opment of children, which was the main reason for restricting
its use in 1976 (Directive 76/769/EEC 1976). Still the pres-
ence of Pb in the surface soil was higher than LSL (400 mg/kg
dw) in six out of ten surface samples and higher than LS
(50 mg/kg dw) in nine out of ten samples, which implies that
lead is still being spread. The high number of wooden boats,
30% of the boats, in this boat club, which differs from most
boat clubs, may explain the very high concentrations of lead in
the soil. Values above 400 mg Pb/kg dw are considered a
health risk by several other authorities, including Thailand
(Maharachpong et al. 2006) and the US EPA (2001). Thus,
the lead values alone own suggest children should avoid this
site and boat owners should take great care in doing mainte-
nance work.
Copper has a long history of use as active ingredient in
antifouling paints and today is the most widely used biocide
for antifouling (Dafforn et al. 2011). This well-known toxicant
affects most organisms negatively in low concentrations.
Many effects of Cu can be found in the literature, see for
example, reviews by Flemmings and Trevors (1989)and
Brooks and Waldock (2009). Tests have mostly been per-
formed on pore water or leachate water. For example, tests
on three nematodes exhibited responses of EC50 around
2 mg/L on reproduction (Boyd and Williams 2003). In our
study, the highest Cu concentrations (0.8 and 0.45 mg/L) were
found in leachates from station D, and these levels would
probably affect nematodes negatively. The toxicity tests
performed on leachate water on soil from this boatyard
indicate that the Cu concentrations found (Table 6)were
partly responsible for the growth inhibition of the alga
C. tenuicorne (Table 8). However, it was not responsible for
the toxic response to the bacteria V. fisheri (Table 7) and did
not negatively affect the larvae development of N. spinipes
(Table 9). Knowledge of the toxic effects of Cu is steadily
increasing and recent work has shown that the chemosensory
systems of fish and other aquatic species may be disturbed at
levels as low as 5–20 μg/L (McIntyre et al. 2012)andin
Daphnia at 7.5 μg/L (Simbeya et al. 2012).
Much of the copper from the boatyard will eventually end
up in adjacent waters (see Turner 2013 and references therein),
and likely, the high copper levels at this boatyard will affect
organisms in nearby waters and make it difficult for them to
thrive. The low levels needed to disturb the chemosensory
systems of organisms indicate that Cu leaking from boat
maintenance facilities may have an even wider effect than
earlier anticipated.
Zinc is commonly used as binder in paints. Zinc concen-
trations in soil pore water have been shown to affect, for
example, soil bacteria with EC50 values of 2.5 and
9.6 mg Zn
2+
/L for Escherichia coli and Pseudomonas
fluorescens,respectively(Chaudrietal.1999). The Zn con-
centrations found in the leachate water from the boatyard are
likely responsible for part of the toxicity observed for all three
test organisms used in this study (Tables 7,8and 9). This
means that leachate water from the soil from boatyards will
leak and probably affect organisms in adjacent waters.
The organotin compounds, TBT, DBT and TPhT, have all
been used as active agents in antifouling paints. Due to their
harmfulness, especially as endocrine disruptors, in 1989, they
were prohibited for use in Europe on boats shorter than 25 m
(Directive 89/677/EEC 1989). Still, very high concentrations
were found even in the surface soil of this boatyard, with a
maximum value of 53 mg (TBT+TPT) at station D. These
high levels are in accordance with what was found in many of
the boatyards by Eklund and Eklund (2013). Thus, very high
J Soils Sediments (2014) 14:955–967 963
levels of organotin compounds seem to be a common feature
on boat maintenance facilities. This is probably caused by the
discarded paint particles that end up on the ground in connec-
tion with boat maintenance, as suggested by Eklund et al.
(2008,2010).
Degradation of TBT and TPhT has been shown to be slow;
it is affected by a number of factors such as density of
microbiological populations, pH, solubility, temperature, light
and oxic properties in the matrix (see, e.g. Dubey and Roy
2003; Antizar-Ladislao 2008). There are few studies on deg-
radation of organotin compounds in soil. Paton et al. (2006)
concluded that biological activity played a key role in degra-
dation of TPhTin agricultural soil. Marcic etal. (2006)studied
degradation of TBT and TPhT in sludge that was added to
agricultural soil. They found that at a pH over 7 and a con-
centration over 100 μg Sn/kg dw, less than 10% of TBT but
about 60% of TPhTwas degraded. We have no pH data on the
soil; nevertheless, the high measured concentrations confirm
that degradation especially of TBT in boatyard soil is a slow
process.
In laboratory studies of marine sediments, the half-life of TBT
was found to be between 360 and 775 days in an oxic environ-
ment; in an anoxic sediment, it took years to decades to degrade
(Dowson et al. 1996; Dubey and Roy 2003). The sediment at this
boatyard was sampled in 2007, and the values showed approx-
imately ten times higher concentrations in the surface sediment
compared to 10 cm deeper in the sediment (Eklund et al. 2008).
This contradicts the findings that degradation is faster in the more
aerobic top sediment. However, a continuous addition of TBT
from the boatyard could explain these figures.
Due to slow degradation of organotin compounds, accumu-
lation may occur in the soil. However, some degradation does
take place as indicated by the relatively high concentrations of
elemental Sn in all samples (Table 2) as compared to back-
ground levels in soil of approximately 3 mg/kg dw (own
observation). The sum of the three most toxic organotins
(DBT, TBT and TPhT) in percentage of elemental Sn is in
the range of 6–29% (Table 3). Somewhat higher percentages of
organotin compounds were found in the deeper samples, which
might indicate a slower degradation due to a possible anoxic
environment (Dubey and Roy 2003; Antizar-Ladislao 2008).
The toxicityof organotin compounds has been described in
numerous reports and all the organism groups studied, from
bacteria to mammals, are affected (e.g. Hoch 2001;Antizar-
Ladislao 2008). TBT is still found in levels that give rise to
imposex in molluscs as was shown in a recent study around
the Korean coast (Choi et al. 2013a). Bioaccumulation of TBT
is indicated by high levels in the liver (average 37 mg/kg wet
weight) of the mammal finless porpoises (Neophocaena
asiaeorientalis) (Choi et al. 2013b). With the high concentra-
tions of organotin compounds at this and other boatyards, the
risk of leaching into to the water is clear. Since TBT is a
prioritized substance, according to the WFD, this is alarming.
Humans risk being exposed to organotin compounds in
connection with maintenance work on paint on pleasure boats.
Most boats today are bought on the used market and the new
boat owner often does not know what type of paints that have
been used on the boat. This means the boat owner may
unknowingly be exposed not only to organotin compounds
but also to different heavy metals and other toxic substances
used in older antifouling paints (e.g. Yebra et al. 2004).
4.3 Cocktail effect
As shown, all the elements and compounds found in the
sample are able to exhibit toxic effects in different organisms.
It should be emphasized that the combined effect is probably
even greater. In this study, the leachate water was only
analysed for Cu, Pb and Zn. However, the test organisms were
exposed to all the compounds in the leachates, which probably
added to the observed effect. For example, TBT has been
shown to be very toxic especially to growth of C. tenuicorne,
with an EC50 of 0.49 μg/L (Karlsson et al. 2006). A strong
correlation (R
2
of 0.88 (p=0.002)) between TBT content and
effect of growth inhibition of C. tenuicorne exposed to har-
bour sediments was found by Eklund et al. (2010), which
further implies toxic effects from organotin substances leaking
from the soil. With the high concentrations of TBT measured
in the soil, it is likely that some has leaked in high enough
concentrations to affect the test organisms and be partly re-
sponsible for the observed toxic effects.
Irgarol has commonly been used as a booster substance in
antifouling paints and specifically affects the photosystem of
plants (Yebra et al. 2004). The EC50 of growth inhibition of
C. tenuicorne was shown to be 0.96 μg/L (Karlsson et al.
2006). Irgarol was found in particularly high concentrations at
station D, and it is likely this leachate might have reached
irgarol levels sufficient to affect the alga.
With the high concentrations of many different pollutants
in the soil, the toxic effect could have been expected to be
even greater. However, most of the pollutants adsorb more or
less firmly to organic material in the soil and do not leach out
easily. This reduces the bioavailable fraction of the toxic
contaminants in the leachate water. This makes it clear that
biological tests should be included in future risk assessment of
boatyard soil.
4.4 Spread of contaminants from boatyards
The paint flakes and dust generated by scraping boats will
usually end up in the ground because, as a rule, the waste is
not collected. Rain results in leaching from the flakes. The
area of paint flakes is significantly greater than when applied
to the boat hull, which accelerates the leaching of metals
(Singh and Turner 2009). Experiments show that the type of
water influences how much of the metals leach from the paint.
964 J Soils Sediments (2014) 14:955–967
Leaching of paint from a painted surface was shown to be
notably higher in artificial seawater than in natural seawater
(Ytreberg et al. 2010). Jessop and Turner (2011)provedthat
leaching was greater in rainwater than in tap water. We used
Milli-Q water to produce leachate water because it has a pH of
5 and a low ion content and thus is quite similar to rainwater.
Our results were comparable to that found in rainwater by
Jessop and Turner (2011). The fraction of Zn leaching from
the soil is around one magnitude higher compared to Cu and
shows that Zn is more easily mobilized, which supports the
data of Jessop and Turner (2011) but contradicts the findings
of Singh and Turner (2009). The observations from these
studies suggest that contaminants may be mobilized from
paint flakes and eventually make an important contribution
to the contamination of adjacent water areas.
Dust is an important means by which contaminants spread
from boatyards. Spread of TBT from boat repair activities was
determined in dust collected from rooftops of houses at Malta
(Decelis and Vella 2007), which suggested that dust from boat
maintenance areas can have impact on adjacent terrestrial
grounds. This correlates well with the findings of lead content
in dust in areas surrounding a boatyard in Thailand where
elevated levels in household dust was found several 100 m
from the boatyard with decreasing distance to the boatyard
(Maharachpong et al. 2006). Much of the dust was transferred
by windblown lead oxide from the boat repair and higher
levels of lead have been detected in the blood of people
living closer to the boatyard than those residing farther
away (Utimanon et al. 2012). Both studies raised the
apprehension that children might be affected and delayed
in their development. The levels found in the soil in this
study were in the same range as found in our study, which show
this is a common problem in and around boat maintenance
facilities.
4.5 Health aspects on working in boat maintenance facilities
In the above discussion, it has been clear that all the contam-
inants measured may pose a hazard to both the environment
and to humans. Other contaminants (PCB, Hg, As, Cd, Cr),
which were not analysed at this boatyard, have been found in
high concentrations in many other boatyards (Eklund and
Eklund 2013). Since the investigated boatyard has been func-
tioning as a maintenance area for 60 years during which many
of these substances were used for preventing organisms from
fouling boats, it is possible these contaminants could be found.
The bio-accessibility of metals in soils and dust contaminated
by marine antifouling paint particles was investigated by
Turner et al. (2009a,b,c). They used an approach that simu-
lates the paediatric gastrointestinal tract described by Ruby
et al. (1996). The authors concluded that the paint dust
contained elevated concentrations of Cu, Cd, Pb and Zn in a
form that is highly bio-accessible, and they recommended
precautions for safe disposal of antifouling residues from boat
maintenance. As discussed, contamination with Pb is consid-
ered a health risk to workers in boat repair and to inhabitants
living near a boatyard (Maharachpong et al. 2006; Utimanon
et al. 2012).
Our soil samples had concentrations in the same levels
as found in boatyard dust by both the Turner group and
the group from Thailand, which implies that the boat
owners might be exposed to hazardous dust that would be
taken up in their guts.
The inherently dangerous properties and the concentrations
being elevated above guidance values show that the soil in the
investigated boatyard, in particular, and boatyards, in general
(Turner 2013; Eklund and Eklund 2013), should be consid-
ered highly polluted. They should not be used for everyday
life and are highly unsuitable places for bringing small children.
Many boatyards are used as camping sites during summer when
the boats are in the sea. This is not recommended due to the risk
of exposure to contaminated dust.
5 Conclusions
The soil in the investigated boatyard is highly polluted by a
number of hazardous compounds such as Cu, Pb, Zn and
organotin compounds (e.g. TBT, DBT and DPhT). Even if
the variation is large within samples, the concentrations for
these pollutants were many times higher than the recommended
guidance values for residential and non-residential areas.
Leachates from the soil were shown to be toxic to test organ-
isms of several trophic orders. This and other studies emphasize
that boatyards are an area that needs to be better regulated to
minimize further spread of contaminants and hazardous expo-
sure to humans. In this work, it is important that guidelines for
TBT in both soil and sediment be agreed upon. The amounts of
contaminants accumulated at boat maintenance facility areas
call for investigations of how remediation should be performed.
Open Access This article is distributed under the terms of the Creative
Commons Attribution License which permits any use, distribution, and
reproduction in any medium, provided the original author(s) and the
source are credited.
References
Abarzua S, Jakubowski S (1995) Biotechnological investigation for the
prevention of biofouling. 1. Biological and biochemical principles
for the prevention of biofouling. Mar Ecol Prog Ser 123:301–312
Almeida E, Diamantino TC, de Sousa O (2007) Marine paints: the
particular case of antifouling paints. Prog Org Coat 59:2–20
Alzieu C (1991) Environmental problems caused by TBT in France:
assessment, regulations, prospects. Mar Environ Res 32:7–17
J Soils Sediments (2014) 14:955–967 965
Alzieu CL, Sanjuan J, Deltreil JP, Borel M (1986) Tin contamination in
Arcachon Bay: effects on oyster shell anomalies. Mar PollutBull 17:
494–498
Antizar-Ladislao B (2008) Environmental levels, toxicity and human
exposure to tributyltin (TBT)-contaminated marine environment.
A review. Environ Int 34:292–308
Boyd WA, Williams PL (2003) Comparison of the sensitivity of three
neamatode species to copper and their utility in aquatic and soil tests.
Environ Toxicol Chem 22:2768–2774
Breitholtz M, Bengtsson B-E (2001) Oestrogens have no hormonal effect
on the development and reproduction of the harpactacoid copepod
Nitocra spinipes. Mar Pollut Bull 42:879–886
Brooks S, Waldock M (2009) The use of copper as a biocide in marine
antifouling paints. In: Hellio C, Yebra D (eds) Advances in Marine
Antifouling Coatings and Technologies. Woodhead Publishing
Limited, Cambridge, pp 492–521
Champ MA (2000) A review of organotin regulatory strategies, pend-
ing actions, related costs and benefits. Sci Total Environ 258:21–
71
Chaudri AM, Knight BP, Barbosa-Jefferson V, Preston S, Paton GI,
Killham K, Coad N, Nicholson F, Chambers BJ, McGrath SP
(1999) Determination of acute Zn toxicity in pore water from soils
previously treated with sewage sludge using bioluminescence as-
says. Environ Sci Technol 33:1880–1885
Choi M, Moon H-B, Yu J, Cho H, Choi H-G (2013a) Temporal trends
(2004–2009) of imposex in rock shells Thais clavigera collected
along the Korean coast associated with tributyltin regulation in 2003
and 2008. Arch Environ Contam Toxicol 64:448–455
Choi M, An Y-R, Park KJ, Lee IS, Hwang D-W, Kim J, Moon H-B
(2013b) Accumulation of butyltin compounds in finless porpoises
(Neophocaena asiaeorientalis) from Korean coast: tracking the
effectiveness of TBTregulation over time. Mar Pollut Bull 66:78–83
Dafforn KA, Lewis JA, Johnston EL (2011) Antifouling strategies:
history and regulation, ecological impacts and mitigation. Mar
Pollut Bull 62:453–465
Decelis R, Vella AJ (2007) Contamination of outdoor settled dust by
butyltins in Malta. Appl Organomet Chem 21:239–245
Directive 76/769/EEC (July 1976) on the approximation of the laws,
regulations and administrative provisions of the member states
relating to restrictions on the marketing and use of certain dangerous
substances and preparations
Directive 89/677/EEC (December 1989) amending for the eight time
Directive 76/769/EEC on the approximation of the laws, regulations
and administrative provisions of the member states to restrictions on
the marketing and use of certain dangerous substances and
preparations
Dowson PH, Bubb JM, Lester JN (1996) Persistence and degradation
pathways of tributyltin in freshwater and estuarine sediments. Estuar
Coast Shelf Sci 42:3–8
Dubey SK, Roy U (2003) Biodegradation of tributyltins (organotins) by
marine bacteria. Appl Organomet Chem 17:3–8
Eklund B (2004) Growth inhibition test with the marine and brackish
water macroalga Ceramium tenuicorne. ITM report no. 131. ISSN
1103-341; ISRN SU-ITM-R-123-SE
Eklund B (2005). Development of growth inhibition test with the marine
and brackish water red alga Ceramium tenuicorne. Mar Pollut Bull
50:921–930
Eklund B, Eklund D (2013) Pleasure boat yard soils are highly contam-
inated. Environment Manage
Eklund B, Elfström M, Borg H (2008) TBT originates from pleasure boats in
Sweden in spite of firm restrictions. Open Environ Sci 2:124–132
Eklund B, Elfström M, Gallego I, Bengtsson B-E, Breitholtz M (2010)
Biological and chemical characterization of harbour sediments from
the Stockholm area. J Soils Sediments 10:127–141
European Chemical Substance Information System (2008) http://esis.jrc.
ec.europa.eu/
Fent K (2006) Worldwide occurrence of organotins from antifouling paints
and effects in the aquatic environment. Handb Environ Chem 5:71–100
Finnie AA (2006) Improved estimates of environmental copper release
rates from antifouling products. Biofouling: J Bioadhesion Biofilm
Res 22:279–291
Finnish Directive (2007) on assessment of contaminated soil and need for
sanitation. (Finska statsrådets förordning om bedömning av markens
föroreningsgrad och saneringsbehov den 1 mars 2007, in Swedish)
Flemmings CA, Trevors JT (1989) Copper toxicity and chemistry in the
environment: a review. Water Air Soil Pollut 44:143–158
Hoch M (2001) Organotin compounds in the environment—an overview.
Appl Geochem 16:719–743
IMO (2001) International convention on the control of harmful anti-
fouling systems on ships, IMO (the AFS Convention). London 19
October 2001
International Standardisation Organisation (ISO) (2007) Water quality—
determination of the inhibitory effect of water samples on the light
emission of Vibrio fischeri (luminiscent bacteria test)—part 3: meth-
od using freeze-dried bacteria. ISO 11348–3:2007
International Standardisation Organisation (ISO) (2010) Water quality—
growth inhibition test with the brackish water and marine macroalga
Ceramium tenuicorne.ISO10710
Jessop A, Turner A (2011) Leaching of Cu and Zn from discarded boat paint
particles into tap water and rain water. Chemosphere 83:1575–1580
Jones B, Bolam T (2007) Copper speciation survey from UK marinas,
harbours and estuaries. Mar Pollut Bull 54:1127–1138
Karlsson J, Breitholtz M, Eklund B (2006) A practical ranking
system to compare toxicity of anti-fouling paints. Mar Pollut Bull
52:1661–1667
Karlsson J, Ytreberg E, Eklund B (2010) Toxicity of anti-fouling paints
for use on pleasure boats and vessels to non-target organisms
representing three trophic levels. EnvironPollut 158:681–687
Kylin H, Haglund K (2010) Screening of antifouling biocides around a
pleasure boat marina in the Baltic Sea after legal restrictions. Bull
Environ Contam Toxicol 85:402–406
Lunn I (1974) Antifouling—A Brief Introduction to the Origins and
Developments of the Marine Antifouling Industry. BCA Publications,
Oxon, Great Britain
Maharachpong N, Geater A, Chongsuvivatwong V (2006) Environmental
and childhood lead contamination in the proximity of boat-repair
yards in southern Thailand—I: pattern and factors related to soil and
household dust levels. Environ Res 101:294–303
Marcic C, Le Hecho I, Denaix L, Lespes G (2006) TBT and TPhT
persistence in a sludged soil. Chemosphere 65:2322–2332
Matthiessen P, Reed J, Johnson M (1999) Sources and potential effects of
copper and zinc concentrations in the estuarine waters of Essex and
Suffolk, United Kingdom. Mar Pollut Bull 38:908–920
McIntyre JK, Baldwin DH, Beauchamp DA, Scholtz NL (2012) Low-
level copper exposures increase visibility and vulnerability of juve-
nile coho salmon to cutthroat trout predators. Ecol Appl 22:1460–
1471
Paton GI, Cheewasedtham W, Marr IL, Dawson JJC (2006) Degradation
and toxicity of phenyltintin compounds in soil. Environ pollut 144:
746–751
Ruby MV, Davis A, Schhof R, Eberie S, Sellstone CM (1996) Estimation
of lead and arsenic bioavailability using a physiologically based
extraction test. Environ Sci Technol 30:422–430
Simbeya CK, Csuzdi E, Dew WA, Pyle GG (2012) Electroantennogram
measurement of the olfactory response of Daphnia sp. and its impair-
ment by waterborne copper. Ecotoxicol Environ Saf 82:80–84
Singh N, Turner A (2009) Trace metals in antifouling paint particles and
their heterogeneous contamination of coastal sediments. Mar Pollut
Bull 58:559–564
Strand J, Jacobsen JA, Pedersen B, Granmo Å (2003) Butyltin com-
pounds in sediment and mollusks from the shipping strait between
Denmark and Sweden. Environ Pollut 124:7–15
966 J Soils Sediments (2014) 14:955–967
Thomas KV, Brooks S (2010) The environmental fate and effects of
antifouling paint biocides. Biofouling 26:73–88
Turner A (2010) Marine pollution from antifouling paint particles. Mar
Pollut Bull 60:159–171
Turner A (2013) Metal contamination of soils, sediments and dust in the
vicinity of marine leisure boat maintenance facilities. J Soils
Sediments 13:1052–1056
Turner A, Singh N, Richards JP (2009a) Bioaccessibility of metals in soils
and dusts contaminated by marine antifouling paint particles.
Environ Pollut 157:1526–1532
Turner A, Pollock H, Brown MT (2009b) Accumulation of Cu and Zn
from antifouling paint particles by the marine macroalga, Ulva
lactuca. Environ Pollut 157:2314–2319
Turner A, Barrett M, Brown MT (2009c) Processing of antifouling paint
particles by Mytilus edulis. Environ Pollut 157:215–220
UN environment program (2008) Interim review of scientific information
on lead. http://www.chem.unep.ch/pb_and_cd/SR/Files/2008/
UNEP-Lead-review-Interim-APPENDIX-mar102008.pdf
US EPA (2001) Residential lead hazards standards—TSCA section 403.
Available at: http://yosemite.epa.gov/opei/rulegate.nsf/byrin/2070-
aj82?opendocument
Utimanon O, Geater A, Chongsuvivatwong V, Saetia W, Verkasalo PK
(2012) Relative contribution of potential modes of surface dust lead
contamination in the homes of boatyard caulkers. J Occup Health
54:165–175
Vindimian É. REGTOX-EV6.xls. Regtox 6.3 software program. Xls,
http://eric.vindimian.9online.fr
Yebra DM, Kiil S, Dam-Johansen K (2004) Antifouling technology—
past, present and future steps towards efficient and environmentally
friendly antifouling coatings. Prog Org Coat 50:75–104
Yebra DM, Kiil S, Weinell CE, Dam-Johansen K (2006) Dissolution rate
measurements of sea water soluble pigments for antifouling paints:
ZnO. Prog Org Coat 56:327–337
Ytreberg E, Karlsson J, Eklund B (2010) Comparison of toxicity and
release rates of Cu and Zn from anti-fouling paints leached in natural
and artificial brackish seawater. Sci Total Environ 408:2459–2466
J Soils Sediments (2014) 14:955–967 967
