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H. Wakeman, C. Eatock / Environmental Pollution
An investigation in to the colonisation rates of marine organisms on
seven varieties of copper based anti-foulant paints.
Helen Wakeman
Dr. Claire Eatock
Falmouth Marine School, Killigrew Street, Falmouth, Cornwall, TR11 3QS, UK
Tel: 01326 311310
Fax: 01326 310300
[email protected]
15, Lister Street
Falmouth
Cornwall
TR11 3BT
H. Wakeman, C. Eatock / Environmental Pollution
An investigation in to the colonisation rates of marine organisms on seven varieties of
copper based anti-foulant paints.
Helen M. Wakeman, Claire Eatock
Marine Science, Falmouth Marine School, Killigrew Street, Falmouth, Cornwall TR11 3QS,
UK
Abstract: Seven varieties of Copper based anti-fouling paints were tested by being applied to
panels. The boards were placed in the Fal Harbour, at Yacht Haven for 5 months, during the
winter season. Bi-weekly measurements of percentage cover upon the panels were recorded
photographically, recording the species most abundant. The investigation concluded the top
three varieties of anti-foul had less that 15% coverage of each panel, which also had the
highest concentrations, and most complex variety of chemicals to ensure this. The products
with the highest levels of percentage cover had low concentrations of elements, and were the
most likely to be worn away first.
Key words
Antifouling paint
Copper
Macroalgae
Toxicity
Bioaccumulation
1. Introduction
The usage of anti-foulant products have been dated back for thousands of years, originally
using copper sheets, which were secured in place with pins made of the same material.
(Readman 2006) The products can help to reduce colonisation upon ships, buoys and other
marine structures of benthic organisms such as invertebrates, micro and macro algaes. It has
been recorded that the use of antifouls has lead to the dispersal and leaching of Cu and Zn
throughout the water system and settling in the local harbours, docking areas and seabed
throughout the world. As much as 2kg of Cu can be discarded per yacht each year. (Boxall et
al., 2000) (Wang. In process) These elements can bioaccumulate and be stored within marine
species such as Ulva lactuca and Mytilus edulis. Biomagnification has been found through
organotin traces found in blood and liver samples of dolphins. (Antizar-Ladislao 2007)
(Hoare 2006)
Antizar-Ladislao, B., (2007) The levels can be higher in areas of low water movement, and
higher levels of CaCO3. (Singh, N., et al 2009) The metals can denature and change the shape
of the cell membrane in macroalgae. All varieties of anti-foul investigated. In this study Cu
as the main source to prevent settlement, as the reaction with seawater creates free ions that
make an unwelcoming environment, as they release biocides. The seven paints used have
diverse levels of chemicals characteristics, which create singular environmental effects that
can be measured through chemical analysis that has to be provided by the companies since
the International Maritime Organisation passed the new regulations in 2008, along with the
commercial ban of Tributyltin. (Readman 2006) (Anti-fouling systems 2002) (Gibert et al
2009)
H. Wakeman, C. Eatock / Environmental Pollution
2. Materials and methods
The method used is similar to that produced by the Marine Biological Association, Plymouth
to determine the quantities and varieties of species growing in one particular area, and the
method used to determine the optimum Cu-free antifoul in the Port of San Diego.
2.1 Sample preparation
Fourteen rectangles of polypropylene panels were formed (140mmx160mmx5mm). Two
holes were placed in each panel symmetrically angled in the top and bottom. Through these
holes the panels can be secured to an area whilst being painted and for drying. The paints
were prepared ready for application, ensuring the entirety of each panel is coated with 2
layers. Two panels should be used to investigate each paint, encase one is lost or damaged
throughout the research. To the bottom of each panel attach a 25g/1oz weight with 0.40mm
15lb fishing line, approximately 100mm in length to ensure the panel does not drift around,
but is held in place. Mark each panel to identify the type of antifoul used with cable ties
(100mmx2.5mm), 1-8. The panels were lowered and secured into the sea until it is below the
water line at low tide.
2.2 Experimental
Photographic samples of both sides of each panel should be taken a minimum of every 3
weeks to ensure the smallest growth can be recorded, measured and compared to previous
measurements. Allow the tags to be included in the photographs to be used for identification.
Throughout a winter investigation a minimum of six months should be allowed, as the cooler
water conditions create a slower, less active environment to that found in summer.
The photographs require cropping and a quadrat (10x10squares) to fit directly overlying each
image. Percentage cover of each panel should be determined, for both sides and recorded.
2.3 Chemical analysis and toxicity
All forms of anti-foulant must have displayed the active substance that is used to deter
organisms growing, ie Cu, in the product description. However, the biocides created from the
reactions within the seawater, and free ions being generated after a biofilm is formed do not
need to be exposed. These types of additional elements to an anti-foul can have a drastic
effect on the settling rate of organisms to any hull. Moreover, the biocides can be toxic to
marine organisms leading to problems of toxicity and death, which can influence the food
web.
3. Results and discussion
The antifouling products have features that make them advantageous in different ways,
whether that it economically, environmentally, or deterring growth of species. Throughout
the bi-weekly surveying a progression rate is measured.
H. Wakeman, C. Eatock / Environmental Pollution
Mean average percentage cover %
Progression of percentage cover
growth on each variety of anti-foul
80
70
FLAG 1
60
FLAG 2
50
FLAG 3
40
INTERSPEED 340 RED
30
INTERCLENE 245 RED
20
INTERSPEED 340 BLACK
10
TRILUX
0
1
2
3
4
5
6
Stages of measuring percentage cover
CONTROL
Fig. 1 A line graph showing the growth progression of percentage cover on panels (2012) Wakeman, H
All the products were in the same conditions throughout the survey, the panel that
demonstrated the highest levels of percentage cover of organisms growing on was the control
panel, it had no form of anti-fouling product on. The starting stages of the eight panels were
very similar for two-three weeks, allowing a biofilm to be created on the boards, for which
the organisms could attach to. The continuing levels of growth maintained a constant until
stage four, the two outstanding values from this were Interclene 245 Red, and Flag test
number 3. The growth was not as exponential as the Control, but still had a dramatic growth
influx of organisms.
Mean average of percentage cover of
organisms growing on the panels
Variety of anti-foul paints
CONTROL
TRILUX
INTERSPEED 340 BLACK
INTERCLENE 245 RED
INTERSPEED 340 RED
FLAG 3
FLAG 2
FLAG 1
0
10
20
30
40
50
60
Mean Average Percentage cover %
Fig. 2. A bar chart showing the average final growth of percentage cover (2012) Wakeman, H
70
80
H. Wakeman, C. Eatock / Environmental Pollution
The chart is showing the mean averages of each type of panels total growth of benthic species
growing on them. The smallest overall growth after the period in the water was achieved by
Trilux 33 red, which was closely followed by Interspeed 340 black, which both had values of
under 10%. The least efficacious product was from Interclene 245 red, closely followed by
Flag variety 3.
Fig. 3 A graph showing the diversity of percentage cover of growth (2012) Wakeman, H
H. Wakeman, C. Eatock / Environmental Pollution
Fig. 4 A box plot graph showing the range of percentage cover (2012) Wakeman, H
Key
A
B
C
D
E
F
G
H
Flag 1
Flag 2
Flag 3
Interspeed 340 Red
Interclene 245 Red
Interspeed 340 Black
Trilux 33 Red
Control
The range from the percentage cover grown on the panel (Fig. 4) is showing the full extent of
the benefits of the paints.
The investigation was tested to be considered scientifically significant, ANOVA was used
which supported the alternative hypothesis, that there is a significant different in the
colonisation rates of organisms that are tested against seven varieties of antifouls.
The box plot charts shows in a visual manor the full growth of species on the individual
panels, displaying where the majority of each growth is on a time scale, also showing where
the anomalies are.
Trilux 3 Red uses Thiocyanic acid Copper(1+) salt, Zinc oxide and Petroleum naphtha as the
main chemicals to reduce the amount of species growth on the panels. Within the marine
system, the Thiocyanic acid hydrolyses to NH3 and CO2. The product can cause disruption of
cell membrane lipids, the cell proteins are broken down, leaving organisms damaged. ZnO is
used to help reduce the corrosion of the framework and hull of a marine vessel. The
negatives side effects of this product will be in altering the reproductive system of organisms
H. Wakeman, C. Eatock / Environmental Pollution
in high concentrations, as well as being a experimental mutagenic. Cuprous (Thiocyanate
2011) (The facts about Ammonia 2004) (Occupational Safety and Health Guidelines for ZnO
2010)
Interspeed 340 Black uses Copper (l) oxide as the main deterrent, the concentrations can
reach 50%, the toxicity can effect not only species that land and settle on the panels, but fish
within the water, daphnia and algae. (Clare 2002) (Algae research 2012) The Ethylene bisdithiocarbamate used as the other active substance is a fungicide, by controlling the algae that
is formed with the use of biocides. (Kjaer 2002) (Pesticide Toxicity 2012)
The Interclene 245 Red product uses Copper (l) oxide, Rosin, Xylene and Zinc oxide in the
highest concentrations. The effects of some of these products on organisms can be to depress
the central nervous system, so if a benthic species would settle on the panels, it would be
affected, in some cases dying, as they are unable to move, catch food or defend themselves,
leaving a carcase. (Occupational Safety and Health Guideline for Xylene 2010) (Toxic
Substances Portal 2011) Whilst simultaneously affecting the settling rate of species on the
panels with high concentrations of Copper.
The Interspeed 340 Red product uses similar active substances to the Black version, stated
above. The highest concentrations are of Copper (l) oxide, Xylene, Zinc oxide and Rosin.
These products can create aquatic toxicity, both chronic and acute affecting a wide range of
marine species, including micro and macroalgae, plankton and fish. (Algae research 2012)
(Clare 2002) The product is a controlled depletion polymer antifouling system, with a high
control of solvent emissions, ensuring the slow release of bi-products. (Interspeed 340 2010)
(Safety Data Sheet 2008)
The Flag paint products use a combination of chemicals that are toxic to aquatic organisms,
but is not counted as a marine pollutant. The products may leave long term effect in the
aquatic environment, potentially creating more adverse effects as it is spread through the
marine system. The products were very similar in the chemical break down, Flag 3 was the
basic formulation that worked on a simply method of relying Copper to create free ions in the
sea water, deterring landing of organisms, this product was least effective. The Flag 1
product had a more successful result, being able to control the landing and establishment of
species more efficiently than the Flag 3. This element had Polytetrafluoroethylene (PTFE)
added into the mixture, this element reduces friction caused by the paint by creating a ‘nonstick’ layer, such as that used in Teflon products. The organisms should not be able to settle,
if they are able to find a area that is not too repelling from the Cu. The final Flag product was
the most successful; this is due to the higher concentrations of Cu and PTFE. The
combination of the two, works symbiotically in a lucrative manor, by reaching just over 10%
overall growth of organisms on the panels which puts it in the top three of the tested paints.
From the study, the paint that worked the best to deter organisms settling on the panels was
Trilux 33 Red. The products that had the least percentage cover used a combination of
complex chemicals, fungicides and PTFE. The Thiocyanic acid Copper(1+) salt was solely
used by Trilux, in this study. Flag 2 used increased quantities of Cu to create a hostile
environment; the free ions send shocks to the organisms, eliminating inhabiting.
The efficiency of the antifoulants is determined by factors that can not be controlled, and
environmental stressors. The levels are in constant flux, even on a 24 hours basis. Such as
the exposure to sun light, temperature of the sea water, salinity of the sea water, geographical
locations and seasons. (Marechal et al 2004) (Wahl et al 2010) (Bao 2008)
The levels of salinity are constantly altering within the Fal, as the estuary allows fresh water
to be passed into the marine system. The leaching of Cu is amplified with higher salinity
levels, and increased CaCO3 present within the water, due to the complex reaction kinetics
H. Wakeman, C. Eatock / Environmental Pollution
that occur when the artificial product mixes with natural seawater. (Singh et al 2009) (Omae
2003)
The paints are constantly working, with means that the duration of their life span is reduced,
resulting some wearing out quicker than others. The Trilux 33 Red worked most efficiently
to deter the organisms from landing, but was one of the first products to be worn away. The
negatives from this are not only will the vessels or structures need to be re-coated quicker, but
with low levels of water movement, such as in the Fal port, there will be higher
concentrations of Cu, as it has dissolved and leached from the products. This will settle
within the sediment, sinking and mixing with marine snow forming a toxic layer to species
that are on the seabed. The oils, silicon and rosins that erode from the antifoulants coat
organisms do not have a toxic effect on organisms, but adsorb the sediment and suspended
particulate matter. Once this is established, the pore water exchange will be blocked, causing
suffocation of the species. (Jones 2007) (Bolam 2007) (Nendza 2007) (Tang et al 2010)
4. Conclusion
The seven varieties of Cu based anti-foulant paints tested showed a significant
difference in the colonisation rates of benthic species, due to the chemical variation in
each product. The most lucrative product was the Trilux 33 Red, closely followed by
Interspeed 340 Black and Flag 2. The least effective products at deterring organisms
from settling were Interspeed 245 Red, Flag 1, Flag 3 then Interclene 245 Red. There
are many factors that can affect the productivity within the marine environment, such as
the light, temperature, salinity and seasons. To investigate further what form of antifoulant product is most environmentally beneficial, more studies should be continued.
H. Wakeman, C. Eatock / Environmental Pollution
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