ASSESSMENT OF ANTIFOULING AGENTS IN COASTAL
ENVIRONMENTS (ACE)
MAS3-CT98-0178
Annual Report (February 1999 – February 2000)
Executive Summary
Significant progress has been achieved during this first year of the ACE programme. All
tasks are on-track with only one exception, the analytical inter-comparison study. This was
postponed until the partners had selected the antifouling agents on which studies would be
focussed. Now that these have been identified (see Sub-task 1.6) the inter-comparison will
be organised. In other areas such as analytical method development (Sub-task 2.1),
environmental surveys (Sub-task 3.1) and ecotoxicology (Sub-task 4.1), progress has
exceeded expectations. In addition, publications in highly reputable journals have already
been achieved. The ACE website has been set up (at www.pml.ac.uk/ace) and a database
constructed using Microsoft Access 97.
Inception/Teambuilding Workshop (workshop 1) – month 1
Responsible:
Project Co-ordinator (PML)
Objectives:
To discuss the overall objectives and agree details of the approach. Final planning for
Task 1. Agree upon the format for the national overviews to be produced (vide infra). To
ensure that the activities at the interfaces between the various tasks and subtasks are well
attuned to each other (e.g. the gathering of information, the setup of the database and the
input needs for the models to be used).
During the inception workshop (workshop 1), tasks will be classified with the participating laboratories to obtain
and compile information on the usage of the antifouling agents registered for each country.
The analytical data obtained will be screened as regards their quality according to the criteria agreed upon
during the inception workshop (workshop 1).
A proposal for the level of detail of the information will be presented to the inception workshop (workshop 1) and
agreed upon and methods for dissemination, e.g. through the Internet, will be discussed.
Delegates:
Steering Committee
Deliverables:
Minutes of meeting.
As scheduled, the meeting was held in Plymouth from 23 to 25 February 1999. The meeting
was successful and achieved the objectives. A meeting report is attached as Annex I.

Task 1
Collection and compilation of information relating to antifouling paint/booster biocide
usage. This is critical to the programme to identify which agents are most used and are
of most concern on a National/local basis to direct methodological/analytical, chemical
surveys and ecotoxicological experiments. The gathering of data will be centralised but
it is likely that usage will be susceptible to high geographical variability.
1
Sub-tasks:
1.1
Surveys of antifouling agents and products being manufactured, imported, used and
marketed (including information about the level of content of the antifouling agents in the
paints and leaching rates) will be conducted.
Sub-task 1.1 – months 2-6
Title
Surveys of antifouling agents and products being manufactured.
Responsible:
PML
Partners:
IVM, CSIC, UILIC, GU, VKI, NERI, IFREMER
Duration:
5 months
Objectives:
To survey antifouling agents and products being used and marketed, including
information about the level of content of the antifouling agents in the paints and all
available information on leaching rates.
Methods:
Each laboratory will assemble details regarding the national usage of antifouling
products. To this end, literature and statistics will be collected relating to manufacture /
registration / importation of products together with information on sales and product
usage.
Deliverables:
Input to database (sub-task 1.4) and major report 1 (sub-task 1.6).
Links:
1.2, 1.4, 1.5, 1.6, 2, 3, 4, 5
All partners have undertaken their national surveys. Negligible data is, however, available
concerning leaching rates of the booster biocides. Details are given in below and are
currently being inputted into the database.
Summary
Inventories conducted (per February 2000):
UK
Inventory of admitted products
yes
Nr of products (paints)
23
Nr of brands
5
Nr of manufacturers
Fr
Gr
Sp
Sw
20
6
Dk
yes
Nl
yes
60
5
5?
20
13
Ingredients admitted small yachts < 25 m (as of 2000)
UK
Fr
Gr
Sp
Sw
Dk
Nl
+
+
+
+
+
a
+
+
Copper (1) oxide
Copper thiocyanate
Cu powder
Zinc oxide
Chromium trioxide
+
+
Diuron
Irgarol 1051
Zinc pyrithione
Dichlofluanid
TCMBT
Chlorothalonil
TCMS pyridine
SeaNine 211
Ziram
Zineb
Folpet
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
a
+
+
+
+
+
?
?
+
+
+
+
+
+
+
+
+
+
+
+
Number of organic boosters
9
5
Notes:
DK: voluntary agreements
a – to be phased out in 6 years (leaching rate regulated)
7
2
4
1
2
5
Partner Reports
Partner 1 - UK
A recent (1998), and thorough survey undertaken by the Water Research centre on behalf of the UK Environment
Agency provides substantial information on usage of booster biocide antifouling agents in the UK (see
Environmental Problems from Antifouling Agents. Survey of Manufacturers, Chandlers (Suppliers) and
Treatment Sites. R & D Technical Reports p215. Research Contractor: WRc plc. Environment Agency, 1998.
ISBN: 1 873160 74 7). They provide the following summary:
“The specific aims of the survey were to: 1) identify the nature of the problem based on usage data; 2)
rank the booster biocides in order to target monitoring in the environment and future method
development; and 3) provide the Environment Agency with information relating to the use and quantities
of antifouling biocides in UK waters.
The project involved an initial pilot study where staff at selected chandlers, boatyards and harbour
authorities were interviewed. On the basis of these interviews a number of questionnaires were compiled
and used to survey chandlers, marina and harbour operators, boatyards and boat owners. Information on
the nature of antifouling products was also obtained from a number of paint manufacturers.
Five main brands of antifouling paint were identified, namely International, Blakes, Jotun, XM Yachting
and Awlgrip and a total of 23 products. The biocides used in these products were copper(1)oxide, copper
thiocyanate, diuron, Irgarol 1051, zinc pyrithione and dichlofluanid. Based on median biocide
concentrations, the rank order of biocide in terms of amount used in antifouling products in the UK was
copper oxide > diuron > copper thiocynanate approximately equal to Irgarol 1051 > zinc pyrithione >
dichlofluanid. The total amount of copper used in the UK in 1 year on UK coastal leisure craft was
estimated at 75173 – 311769 kg. Previous estimates provided by the British Coatings Federation (ACP,
1995) were 130000 kg.
Whilst a biocide may be used in large quantities, this does not necessarily mean that it will be the
predominant biocide in the environment. The reason for this being that the environmental concentrations
are primarily dependent on the amounts of biocide emitted to the environment during paint application
and removal and through leaching. The main method of paint removal was water-blasting and data were
available on likely emissions of copper during the water-blasting process. Using these data along with an
estimate of the number of leisure craft in UK coastal waters, it was estimated that between 6.4 and 420 kg
of copper will enter the environment in one year as a result of paint removal. This quantity is
significantly less than estimated emissions through leaching (i.e. 26294 and 109502 kg yr -1).
Whilst no information was available on the leaching rates of diuron, zinc pyrithione and dichlofluanid,
data were available for Irgarol 1051. Using these data it was estimated that between 1793 and 28031 kg
of Irgarol 1051 leaches into the environment in one year. The upper value is greater than the estimates of
the actual amount of Irgarol 1051 used in antifouling paints in one year. The likely reason for this is the
large range of leaching rates that are reported for Irgarol 1051 (i.e. 2.5 – 16 μg cm-2d-1).
Likely concentrations of each of the biocides in a marina were also estimated using the modelling
approach developed by Linders and Luttik (1995). Using the default values recommended in the model
along with data from the survey on the proportion of boats treated with each biocide, concentration ranges
of 127 – 254 μg1-1 for copper, 8.65 – 9.9 μg1-1 for diuron, 5.43 – 41.2 μg1-1 for Irgarol, 70 – 449 ng 1-1
for zinc pyrithione and 23 – 34 μg1-1 for dichlofluanid were obtained. In general these are more than an
order of magnitude higher than the toxicity values reported. However, the estimated Irgarol 1051, diuron
and copper concentrations were generally higher than levels measured previously in the marine
environment (Lord et al., 1997; Lewis and Gardiner, 1995: ACP, 1995), the predictions of concentrations
in marina waters were therefore probably an overestimate.”
3
Table 1 Outline of approach used for antifouling usage survey (UK)
Survey Group
Number
Of samples
Information
Source
Survey
Medium
Questions
Asked
Aim
Biocide
Manufacturers
3(2)
Paint
Manufacturers
T


Environmental fate and behaviour of biocides
leaching rates

Paint
Manufacturers
4(2)
Chandlers,
International
T,I





paints sold in UK
concentration of active ingredients
total amount of pain sold/year
leaching rates
sales information



usage information
ranking of actives
potential inputs to environment
Chandlers
50(50)
Sail and Power
Nautical
Almanac (1998)
T,P,I




paints sold
total amounts sold
paints recommended
sales patterns


regional usage information
usage patterns
Harbours/Marinas
50(50)
Sail and Power
Nautical
Almanac (1998)
T,P,I


size distribution of boats
types of boats

calculation of inputs on regional basis
Boatyards
50(50)
Sail and Power
Nautical
Almanac (1998)
T,P,I




number of boats antifouled
types of boat antifouled
sizes of boats antifouled
types of paint used

usage patterns related to boat types
Shipyards
1(1)
T
number of vessels antifouled
size of vessels antifouled
types of pain used
Boat owners
500(390)








size and type of boat
antifouling used
frequency of antifouling
method of antifouling


usage patterns relating to boat type
calculation of inputs on local scale
Royal
Yachting
Association
1
T


number of boats afloat in the UK
number of marine berths

calculation of inputs on a national scale
British
Industries
1
T



number of chandlers in the UK
number of boatyards/marinas
numbers of vessels afloat

calculation of inputs on a national scale
Marine
Royal Yachting
Association
P
T = Telephone interview; P = Postal survey; I = Face to face interview
4
information to obtain indication of amounts of
biocide entering the aquatic environment
Currently, nine booster biocides are approved for use in amateur and professional antifouling producing, namely:









zinc pyrithione
TCMTB (2-thiocyanomethyl-benzothiazole)
kathon 5287
TCMS pyridine (2,3,5,6-tetrachloro-4-sulfuronyl pyridine)
Irgarol
diuron
dichlofluanid
chlorthalonil
zineb
NB: The booster biocides, thiram, ziram and maneb are no longer approved for use although some may be in the
supply chain.
The survey undertaken by WRc took the approach outlined in Table 1. Full details and results are given in their report.
Results most pertinent to the ACE programme follow:
Brands
Five main brands of antifouling paint were identified, namely International, Blakes, Jotun, XM Yachting and Awlgrip
(Table 2). International had the largest share of the market (Figure 1) with an average chandler selling approximately
550 litres and an average boatyard using 99 litres of International paint in one year. There were some differences in the
paint brands sold by chandlers and those used by boatyards, the main difference being for the Jotun brand where
chandlers only sold small quantities whereas boatyards used similar amounts to the Blakes brand.
The majority of paints were sold and used between February and May. The most popular paint colours being red, blue,
Dover white and navy.
Manufacturer
Products
International
Micron CSC, Cruiser Superior, Cruiser premium, Interspeed Extra Strong, Interspeed
2000, Micron Optima
Blakes
Sea Tech, Titan FGA, Tiger Cruising, Hard Racing, Lynx Plus. Broads Freshwater,
Pilot
Jotun
Supertropic, Super, Non-Stop, Racing, Aqualine
XM Yachting
C2000, HS3000, P4000
Awlgrip
Awlstar Gold Label
Table 2
Manufacturers contacted in the survey and their products (UK)
5
60
Percentage
48
36
24
12
0
International
Figure 1
Blakes
Jotun
1
Brand
XM
Other
Percentage of each antifouling paint brand used by boat owners (open bars), chandlers
(hatched bars) and boatyards (cross hatched bars) (UK)
Products
Chandlers sold more than 23 types of antifouling paint, whereas the boatyards surveyed used on 18 products (Figure 2).
The most popular products sold by chandlers were Cruiser Premium (International), Tiger Cruising (Blakes), Micron
CSC (International) and Cruiser Superior (International). These products, along with Supertropic (Jotun) were also
favoured by boatyards.
The biocides contained in each of the products are detailed in Table 3.
From the data collated by WRc, they estimate the quantities of antifouling biocides distributed/used in the
UK/year. These values are listed in Table 4.
Maximum Amount (kg yr-1)
copper(1)oxide
copper thiocyanate
diuron
Irgarol 1051
zinc pyrithione
dichlofluanid
311769
4216
24738
10186
8246
388
Minimum Amount (kg yr-1)
75173
282
3288
59
1369
153
Table 4: Estimated the quantities of antifouling booster biocide distributed/used in the UK per year
Leaching rates
The EA report lists the following leaching rates:
Irgarol
Copper(1)oxide
Copper thiocyanate
:
:
:
2.5 – 16 μgcm-2d-1
10 – 20 μgcm-2d-1
10 – 20 μgcm-2d-1
6
Table 3
Antifouling
Product
Micron CSC
Cruiser Superior
Cruiser Premium
Interspeed Extra Strong
Interspeed 2000
Waterways
Micron Optima
VC System
Prop O Drev TF Black
Sea Tech
Titan FGA
Tiger Cruising
Hard Racing
Lynx Plus
Broads Freshwater
Pilot
Hempel (tin free)
Supertropic
Super
Non-Stop
Racing
Aqualine
C2000
HS3000
P4000
Awlgrip
Marclear
VC Offshore
Colour
Red base
Red activator
Red
Grey
Grey
Black
White
Black
Blue
Grey
Black
Blue
Green
Red
Concentration ranges (% w/w) of biocides in antifouling paint products (UK)
Density
Copper
Oxide
1.6
1.35
1.6
1.5
1.3
1.5
2.2
25-50
10-25
10-25
25-50
Copper
Thiocyanate
Diuron
Irgarol
1051
Zinc
Pyrithione
Dichlofluanid
2.5-10
2.5-10
1-2.5
1-2.5
10-25
0-2.5
2.5-10
50-100
10-25
1.38
0.80
1.7
1.8
1.9
1.8
1.9
50-100
1.7
1.7
1.6
1.6
1.5
1.4
20-40
20-40
5-10
30-50
20-40
20-40
20-40
20-50
15-20
1.5
1.6*
1.6*
1.6*
1.6*
1.6*
1.6*
1.6*
1.6*
1.6*
1.6*
1.6*
1.6*
0-50
2-5
20-50
0.1-5.0
0.1-5.0
0.1-5.0
0.1-5.0
0.1-5.0
0.1-5.0
0.5-2.0
0.5-2.0
0.1-5.0
20-30
10-30
#
21.16
10.1-41.3
33.0-35.0
32-35
0.1-5.0
0.1-5.0
#
25
30
30
42.48-46.47
#
1.0
1.0
1.0
2-10
2-10
1.35-1.53
#
* - data not available, so mean density of all other products value used
# - biocide present in product but information on concentrations not available
7
#
0
0
Figure 2
Non Stop
Racing
Titan FGA
Super
Micron Optima
Sea Tech
Supertropic
Pilot
Awlgrip
Interspeed 2000
Waterways
Broads FW
Tiger Cruising
P4000
6
Interspeed ES
12
Lynx Plus
18
HS3000
24
Cruiser Premium
30
Hard Racing
6
C2000
12
Cruiser Superior
Aqualine
Percentage
0
Micron CSC
Percentage
Percentage
18
12
6
Percentage of antifouling products used by boat owners (open bars and boatyards (cross
hatched bars) or sold by chandlers (hatched bars) (UK)
8
Partner 2 - Netherlands
The admission of antifouling biocides in The Netherlands is regulated by the “College voor Toelating van
Bestrijdingsmiddelen” (CTB) in Wageningen. On their web-site (http://www.bib.wau.nl/ctb/) information is available
on the admission of products and the restriction of their use in certain application areas. The data collected from the
web site is compiled into a data base from which a table is constructed containing the admitted products, their
manufacturers and their active ingredients (Table 5). The numbers between brackets represent the CTB admission
numbers (CTB, 1999).
60 products are admitted in The Netherlands as antifouling paint. 45 products were non-tin products and there is only 1
product that does not contain any (organo)metallic active ingredient, i.e., Chloorrubber Antifouling which contains
dichlofluanid as the active ingredient. 35 out of the 59 (organo)metallic containing products (mainly cupric oxide) also
contain booster biocides like Irgarol 1051, Diuron, Zineb, Ziram and Dichlofluanid.
Figures on the sales and use of the antifouling products in The Netherlands are not readily available. To gain insight
into which manufacturers are active on the Dutch market, a major national boating/yachting trade exhibition was
visited, i.e. the HISWA 1999, in the RAI-exhibition centre in Amsterdam. Major stand-holders are listed below;
INTERNATIONAL PAINT (NEDERLAND) B.V.
KLEIDIJK 88
3161 HJ RHOON
SIGMA COATINGS B.V.
HEMPEL COATINGS (NEDERLAND) B.V.
JAMES WATTWEG 2
3133 KK VLAARDINGEN
LAK- EN VERFFABR. W. HEEREN & ZOON
B.V.
OOSTEINDERWEG 32
1432 AL AALSMEER
AMSTERDAMSEWEG 14
1422 AD UITHOORN
AKZO COATINGS B.V.
RIJKSSTRAATWEG 31
2171 AJ SASSENHEIM
To gain information on popular products, a chandler was visited near the largest Dutch marina, i.e., Seaport Marina
IJmuiden. The following 5 products were most frequently sold: diuron, Irgarol, dichlofluanid, ziram and zineb.
A survey on the antifouling biocides admitted in the Netherlands showed that 5 organic compounds are currently
registered for use as antifouling agents, i.e. diuron, irgarol 1051, dichlofluanid, ziram and zineb. Figures on shipping
traffic on the NCP showed that less than 40% of the ships originate from the Netherlands. This indicates that a large
part of the ships that visit the harbours along the Dutch coast originate from other countries in which a different
admittance policy might be conducted.
The results from a survey on the distribution of yacht havens, shipping intensities and sluice passages were combined to
identify the areas most relevant with regards to the contamination by antifouling agents. The following locations were
selected; Harlingen, Den Helder, IJmuiden, Katwijk, Hoek van Holland, Roompot sluis and Vlissingen. These locations
will be monitored during a period of at least one year (March 2000 till March 2001).
9
Table 5 Antifouling products admitted in the Netherlands
Dichlofluanide
Ziram
Zineb
Diuron
10
Irgarol
FORTIS 505 ANTIFOULING (11565)
HEMPEL' S MILLE DYNAMIC L 71700 (11934)
HEMPEL'S ANTIFOULING CLASSIC 76540 (11524)
HEMPEL'S ANTIFOULING CLASSIC 7655 (9662)
HEMPEL'S ANTIFOULING COMBIC 71990 (11458)
HEMPEL'S ANTIFOULING COMBIC 7199B (11419)
HEMPEL'S ANTIFOULING COMBIC 76990 (11937)
HEMPEL'S ANTIFOULING COMBIC 7699B (11528)
HEMPEL'S ANTIFOULING NAUTIC 7190B (11418)
HEMPEL'S ANTIFOULING NAUTIC HI 71900 (11089)
HEMPEL'S ANTIFOULING NAUTIC HI 7690 B (11814)
HEMPEL'S ANTIFOULING NAUTIC-HI 7690 (9661)
HEMPEL'S HARD RACING 76480 (11932)
HEMPEL'S HIGH SPEED HARD RACING TIN FREE 7648.1
HEMPEL'S MILLE DYNAMIC 7170-1 (10449)
HEMPEL'S MILLE DYNAMIC H 71700 (11935)
HISOL INTERSMOOTH (9282)
INTERCLENE BCA 300 PREMIUM (10430)
Chromiumtrioxide
EPIFANES ZELFSLIJPENDE ANTIFOULING (11758)
Copperthiocyanate
x
Copper
VAN SWAAY SCHIJNDEL B.V
AKZO NOBEL COATINGS B.V
INTERNATIONAL PAINTS
AMERON B.V.
LAK- EN VERFFABR. W.
HEEREN & ZOON B.V.
LAK- EN VERFFABR. W.
HEEREN & ZOON B.V.
FORTIS COATINGS B.V.
HEMPEL COATINGS
HEMPEL COATINGS
HEMPEL COATINGS
HEMPEL COATINGS
HEMPEL COATINGS
HEMPEL COATINGS
HEMPEL COATINGS
HEMPEL COATINGS
HEMPEL COATINGS
HEMPEL COATINGS
HEMPEL COATINGS
HEMPEL COATINGS
HEMPEL COATINGS
HEMPEL COATINGS
HEMPEL COATINGS
INTERNATIONAL PAINTS
INTERNATIONAL PAINTS
Tributyltinpolymer
x
x
x
x
x
x
Tributyltinmethacry
late
CHUGOKU PAINTS B.V.
JOTUN B.V.
JOTUN B.V.
JOTUN B.V.
NOF EUROPE N.V.
NOF EUROPE N.V.
Tributyltinoxide
Copper(1)oxide
AF SEAFLO Z-100 LE-HS (NB) (11064)
ANTIFOULING SEAGUARDIAN (10593)
ANTIFOULING SEAVICTOR 40 (11244)
ANTIFOULING SUPER TROPIC (10594)
AWLGRIP AWLSTAR GOLD LABEL ANTI-FOULING (11256)
AWLGRIP AWLSTAR GOLD LABEL ANTI-FOULING BP 501
LIGHT BLUE (11257)
CELFIX OX (11381)
CHLOORRUBBER ANTIFOULING 2000 (10692)
CRUISER SUPERIOR (10975)
DEVOE ABC NO. 3 ANTIFOULING (11925)
EPIFANES BRONS BOTTOM PAINT (9577)
Tributyltinfluoride
Manufacturer
Zincoxide
Product Name
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
Dichlofluanide
x
x
x
Ziram
x
x
x
Zineb
Diuron
Irgarol
11
Chromiumtrioxide
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
Copperthiocyanate
INTERNATIONAL PAINTS
INTERNATIONAL PAINTS
INTERNATIONAL PAINTS
INTERNATIONAL PAINTS
INTERNATIONAL PAINTS
INTERNATIONAL PAINTS
INTERNATIONAL PAINTS
CHUGOKU PAINTS B.V.
CHUGOKU PAINTS B.V.
CHUGOKU PAINTS B.V.
SIGMA COATINGS B.V., RPIC
SIGMA COATINGS B.V., RPIC
SIGMA COATINGS B.V., RPIC
SIGMA COATINGS B.V., RPIC
SIGMA COATINGS B.V., RPIC
SIGMA COATINGS B.V., RPIC
TOUWEN & CO B.V.
INTERNATIONAL PAINTS
INTERNATIONAL PAINTS
INTERNATIONAL PAINTS
INTERNATIONAL PAINTS
INTERNATIONAL PAINTS
AKZO NOBEL COATINGS B.V.
INTERNATIONAL PAINTS
LAK- EN VERFFABR. W.
HEEREN & ZOON
Copper
INTERSPEED (12022)
INTERSPEED (BRA 140) (10429)
INTERSPEED 340 (11858)
INTERSPEED EXTRA STRONG (12023)
INTERSPEED SYSTEM 2 (10290)
INTERVIRON SUPER TIN-FREE SPC (12021)
MICRON CSC (10976)
RAVAX AF (11532)
SEA TENDER 10 (12029)
SEA TENDER 7 (12028)
SEAFLO 15 (11063)
SIGMA PILOT ECOL ANTIFOULING NL (11717)
SIGMAPLANE ECOL ANTIFOULING 1154 (11459)
SIGMAPLANE HA ANTIFOULING (10501)
SIGMAPLANE HB ANTIFOULING (11113)
SIGMAPLANE TA ANTIFOULING (9905)
TENCO SCHOONSCHIP ANTIFOULING TEERVRIJ (11800)
VC 17M EP ANTIFOULING (11402)
VC AQUA 12 (10948)
VC OFFSHORE EXTRA (11564)
VC PROP O DREV, BLACK (10995)
VC PROP O DREV, GREY (10996)
VINYL ANTIFOULING 2000 (11648)
WATERWAYS ANTIFOULING (9691)
WERDOL ANTIFOULING TINVRIJ (10589)
x
x
x
Tributyltinpolymer
x
x
x
x
Tributyltinmethacrylate
INTERNATIONAL PAINTS
INTERNATIONAL PAINTS
INTERNATIONAL PAINTS
INTERNATIONAL PAINTS
Tributyltinoxide
INTERSMOOTH 120 PREMIUM (11706)
INTERSMOOTH 210 (11728)
INTERSMOOTH 220 PREMIUM (11705)
INTERSMOOTH HISOL 2000 (10289)
Tributyltinfluoride
x
Zincoxide
INTERNATIONAL PAINTS
Manufacturer
Copper(1)oxide
INTERCLENE SUPER BCA 400 (10590)
Product Name
Leaching rates of antifoulants
Experimental determinations of leaching rates are usually conducted by manufacturers during the development and testing phases
of new products, usually according to ASTM protocols. The results from these experimental studies cannot be translated to reallife leaching rates from ships to which the product is applied. Available protocols have been criticised by various authors (Berg,
1995). For many of the new products, established and certified analytical methods are hardly available (Thomas, 1998). To date,
no field studies with painted ships have been published in the open literature.
Leaching rate estimates used in a brief selection of recent experimental or risk-assessment studies have been summarised in Table
6. For each compound a broad range of leaching rate estimates are observed. Copper leaching rates are usually higher than for
other compounds. Leaching rates reported for TBT are usually below regulatory implied values of 4 g/cm2/day in some
countries (USA, Sweden). A comprehensive review leaching rates is beyond the scope of this study.
Compound
TBT
Cu
Irgarol
DCOI
Leaching rate
g/cm2/day
4
2.5
0.1 – 5
1.3 – 3.0
6.2
1-20
8 – 25
37 – 101
4–6*
2 – 16
5
1 (0.1 – 5)
Table 6.
*
Type of study
Author
North Sea
Marina
Harbour
Ships > 25m
Marina
Not specified
Ships >12m
Ships > 25m
Exp. study
Marina
Marina
Harbour
Stronkhorst et al. (1996)
Johnson and Luttik (1996)
Willingham and Jacobson (1996)
Lindgren et al. (1998)
Matthiesen and Reed (1997)
Hare (1993)
Lindgren et al. (1998)
Lindgren et al. (1998)
Berg (1995)
Ciba (1995)
Scarlett et al. (1997)
Willingham and Jacobson (1996)
Summary of leaching rate estimates used in various studies.
after 21 days. During the first 21 days leaching rates ranged between 7 – 61 g/cm2/day.
For the Mam-Pec model the following default leachng rates were derived, based on the expertise available within the CEPE
Antifouling Working Group
Copper
TBT
Other biocides
50 g/cm2/day
4 g/cm2/day
2.5 g/cm2/day
Partner 3 - Spain
Copper based antifouling biocides with Irgarol , diuron and SeaNine are thought to be the most widely used
on leisure craft in the different marinas in Spain. Over the last year, an increase in the use of diuron,
dichlofuanid and SeaNine has been observed whereas the use of Irgarol has decreased.
Partner 4 Greece
A survey of antifouling agents and related products on the Greek market was performed from March to June 1999. Thirteen (13)
small Greek companies are involved in the trade and promotion of the target products. Most of them are located in the Athens area.
The antifouling paints used in Greece are based on the following biocides: Irgarol 1051, copper (1)oxide, 4-m-chloro-cresol,
diuron, zinc pyrithione and dichlofluanid.
12
Partner 5 - Sweden
Laws and regulations
In Sweden, toxic antifouling paints fall under the laws concerning biocides, thus no antifouling paint containing toxic substances
may be used until it is aproved by the Swedish National Chemicals Inspectorate, KEMI.
In 1992 they approved 20+ antifouling paints containing copper and Irgarol for use until the end of 1996. Even though the
environmental risks were considered high, the KEMI saw no other acceptable alternatives at the time.
In the decision, the KEMI also stated that since the antifouling paints were highly toxic they should, in the long run, be exchanged
for environmentally safer alternatives. To lessen the risks during the interim time until such alternatives were developed and
introduced to the market and since the copper load in the waters of the Swedish eastcoast were close to the point where serious
damage to the aqutic biota could be expected, the KEMI chose to differentiate between the west- and the east-coast of Sweden. By
limiting the leakage of the first 14 days after launching, the acute toxic effects are reduced in the spring and early summer when
many boats are launched to sea. KEMI approved only paints with a copper leakage of less than 150 µg Cu/cm 2 the first 14 days
on the Swedish westcoast and paints with less than 75 µg/cm2 on the eastcoast. No approval was given for use of antifouling
paints in freshwater lakes or in the Bay of Botnia. No paint with a higher leakage rate was approved. There were no limits set for
Irgarol leakage.
During the years 1997 – 1999, only paints which had had their documentation completed with leakage studies and significant
ecotoxicological studies have been approved.
From the first of January 2000, the use of Irgarol in antifouling paints has become highly restricted. During the years 2000-2001,
only antifouling paints which leak less than 200 µg/cm2 copper during the first 14 days and release less than 350 µg/cm2 until day
30 will be approved. There are no restrictions for the use of Irgarol. After the year 2001, evaluations will be made of the existing
non-toxic alternatives for fouling control. If the Swedish National Chemicals Inspectorate, KEMI, judge that alternative non-toxic
methods are easily avaliable as substitutes for antifouling paint, all toxic antifouing paints will be banned. Currently six
antifouling paints are approved for use on the Swedish westcoast only. Three of them contain 0.6 – 0.8 % Irgarol, while the
remaining three do not contain Irgarol.
On the Swedish eastcoast no toxic antifouling paints will be approved after the first of January 2000.
Usagepattern
In 1997, the KEMI investigated the observance of the rules and thus asked the local authorities to map the usage of antifouling
paints in their district. Most local authorities have chosen to check the sales and try to inform about the rules since the practical
difficulties involved in actually controlling use of antifouling paints were considered too big.
On the eastcoast south of Örskär, observance of the rules are deemed good even though some westcoast-quality paints are sold in
the southern Baltic sea area and there are suspicions of widespread missuse in some areas. North of Örskär the observance are
relatively good with few indications of misuse. In the freshwater lakes, especially in lakes with connection to the sea, use of
eastcoast-quality paints are considered relatively high.
Sales of westcoast-quality paint in the freshwater lakes and in the Baltic, north of Örskär are small and declared to be reserved for
boat owners with boats on the westcoast only.
Sales and Use
In 1997, the amount of antifouling paint sold was slightly less than 181000 litres, which is a small decrease since the years before.
Sales of westcoast-quality paint were relatively constant, while the trend of sales for eastcoast quality paint decreased. Twenty
percent of the sales in 1997 (approx. 36000 liters) were of westcoast quality and the remaining 145000 were eastcoast quality.
Information has been derived from: Eriksson, U. Lindgren, P. Olsson, B. and Unger, C. (1998) “Antifoulingprodukter,
Fritidsbåtar” Kemikalieinspektionen, Biocidprocessen, PM-Beslut 1998-02-24, rev. 1998-12-18
National Chemicals Inspectorate, KEMI (Stockholm)
Antifouling paints
Approved paints 2000-02-01 are listed in Table 7. Number of paints: 41
13
Table 7. Antifouling Paints (Sweden)
Paints intended for pleasure craft
Paints intended for Commercial Vessels
Cruiser
2-tert-Butylamino-4-cyklopropylamino-6methylthio-1,3,5-triazine2.3 % per weight
Copperthiocyanate 5.9 % per weight
Sargasso AL KNM
2-tert-Butylamino-4-cyklopropylamino-6methylthio-1,3,5-triazine 2 % per weight
Copperthiocyanate 26 % per weight
Cruiser White
2-tert-Butylamino-4-cyklopropylamino-6methylthio-1,3,5-triazine 2 % per weight
Copperthiocyanate 5 % per weight
Antifouling Seaconomy S2
Copper(I)oxide 9.6 % per weight
Tributyltinmethacrylate copolymere 18 % per
weight
bis(Tributyltin)oxide 0.4 % per weight
Fabi
Copper(I)oxide 6 % per weight
Trilux
2-tert-Butylamino-4-cyklopropylamino-6methylthio-1,3,5-triazine 2.1 % per weight
Copperthiocyanate 5.4 % per weight
Trilux White
2-tert-Butylamino-4-cyklopropylamino-6methylthio-1,3,5-triazine 1.8 % per weight
Copperthiocyanate 4.8 % per weight
V P - Antifouling
2-tert-Butylamino-4-cyklopropylamino-6methylthio-1,3,5-triazine 0.8 % per weight
Copperthiocyanate 5.9 % per weight
VC 17 New Technology
2-tert-Butylamino-4-cyklopropylamino-6methylthio-1,3,5-triazine 0.6 % per weight
Copper pulver 14 % per weight
VC Prop-o-Drev
2-tert-Butylamino-4-cyklopropylamino-6methylthio-1,3,5-triazine 0.8 % per weight
Copperthiocyanate 5.9 % per weight
Yacht Classic S
Copper(I)oxide 10 % per weight
Yacht Classic S II
Copper(I)oxide 6 % per weight
Micron WQ
2-tert-Butylamino-4-cyklopropylamino-6methylthio-1,3,5-triazine 2.1 % per weight
Copper(I)oxide 5.5 % per weight
Antifouling Seaguardian
Copper(I)oxide 42 % per weight
Antifouling Seamate FB 30
Copper(I)oxide 14 % per weight
Tributyltennmethakrylat copolymer 19 % per
weight
bis(Tributyltin)oxide 0.4 % per weight
Antifouling Seamate SB 33
Copper(I)oxide 14 % per weight
Tributyltennmethakrylat copolymer 18 % per
weight
bis(Tributyltin)oxide 1 % per weight
Antifouling Seavictor 40
Copper(I)oxide 42 % per weight
Antifouling Seavictor 50
4,5-Dichloro-2-n-octyl-4-isothiazoline-3-one 2
% per weight
Copper(I)oxide 40 % per weight
Antifouling Super Tropic
Copper(I)oxide 26 % per weight
Antifouling Super Tropic-F
Copper(I)oxide 26 % per weight
Hempel´s Antifouling Mille Alu 7160
2-tert-Butylamino-4-cyklopropylamino-6methylthio-1,3,5-triazin 3.5 % per weight
Copperthiocyanate 19 % per weight
Interclene BCA 400-serie
Copper(I)oxide 32 % per weight
Intersmooth BFA 230-serie
Copper(I)oxide 36 % per weight
Tributyltennmethakrylat copolymer 17 % per
weight
bis(Tributyltin)oxide 0.5 % per weight
Interspeed Extra BWO 500 Röd
2-tert-Butylamino-4-cyklopropylamino-6methylthio-1,3,5-triazine 2 % per weight
Copper(I)oxide 31 % per weight
Interspeed Premium Antifouling Blac
2-tert-Butylamino-4-cyklopropylamino-6methylthio-1,3,5-triazine 2.3 % per weight
Copperthiocyanate 18 % per weight
Interswift BKA 040-serie
Copper(I)oxide 37 % per weight
Tributyltennmethakrylat copolymer 17 % per
weight
bis(Tributyltin)oxide 0.5 % per weight
Interviron BQA 100-serie
Copper(I)oxide 56 % per weight
Interviron Super
2-tert-Butylamino-4-cyklopropylamino-6methylthio-1,3,5-triazine 2.7 % per weight
Copper(I)oxide 43 % per weight
Interviron Super BQO 405
2-tert-Butylamino-4-cyklopropylamino-6methylthio-1,3,5-triazine 2.4 % per weight
Copper(I)oxide 38 % per weight
Seaflo 15
Copper(I)oxide 28 % per weight
Tributyltennmethakrylat copolymer 27 % per
weight
bis(Tributyltin)oxide 0.7 % per weight
Seatender 10
Copper(I)oxide 37 % per weight
Hempel's Antifouling Classic S 7611
Copper(I)oxide 10 % per weight
Shiranami - Vit Våg
Copper powder 20 % per weight
Micron WQ White
2-tert-Butylamino-4-cyklopropylamino-6methylthio-1,3,5-triazine 1.9 % per weight
Copper(I)oxide 5 % per weight
Hempel's Antifouling Nautic 7190
2-tert-Butylamino-4-cyklopropylamino-6methylthio-1,3,5-triazine 2.6 % per weight
Copper(I)oxide 42 % per weight
Sigmaplane Ecol Antifouling
Copper(I)oxide 49 % per weight
Mille Dynamic
2-tert-Butylamino-4-cyklopropylamino-6methylthio-1,3,5-triazine 3.5 % per weight
Copperthiocyanate 17 % per weight
Hempel's Antifouling Nautic SP-ACE
Copper(I)oxide 43 % per weight
Tributyltennmethakrylat copolymer 13 % per
weight
bis(Tributyltin)oxide 0.6 % per weight
Hempel's Antifouling Nautic SP-ACE
Copper(I)oxide 46 % per weight
Tributyltennmethakrylat copolymer 10 % per
weight
bis(Tributyltin)oxide 0.6 % per weight
14
Sigmaplane HB Antifouling
Copper(I)oxide 28 % per weight
Tributyltennmethakrylat copolymer 19 % per
weight
bis(Tributyltin)oxide 0.5 % per weight
Sigmarine Antifouling
Copper(I)oxide 27 % per weight
National Chemicals Inspectorate, Box 1384,
171 27 Solna * e-mail: kemi@kemi.se * 08783 11 00 * fax 08-735 76 98
Partners 6&7 - Denmark
A recent Danish inventory (NERI) on antifouling compounds legally used on boats of less than 25 metres of length was published
in 1998 (Danish EPA report No. 384, 1998). The survey included manufacturers information on the Danish antifouling market
including TBT.
Antifouling agents and products used in Denmark:
Active compound used
TBT
Diuron®
Irgarol 1051®
SeaNine®
Zink omedin®
Copper
Product mainly used for
Commercial ships > 25 meters length
Boats < 25 length
Boats < 25 length
Full range
Full range
In most antifouling paints
Comment
In combination with Cu
In combination with Cu
In combination with Cu
In combination with Cu
In combination with Cu
Table 8. The highest volume antifouling booster biocides listed for use in Denmark 1997.
The most important manufacturers of products on the Danish market are:

J. C. Hempel A/S

International marine paints,

Jotun marine paints

Sigma marine coatings
The amounts of antifouling compounds were collected when a minimum of 3 manufacturers /distributors were ready to submit
their figures. However, it is important to note the high uncertainty of the figures especially for Irgarol and Diuron. The high
fluctuations were due to restrictions in the uses of both products, where Irgarol was barred for use and substituted by Diuron.
Copper is also included in this survey as it is the base of almost all antifouling paints for most vessels with the exception of
aluminium hulled boats.
Compound
TBT
Diuron®
Irgarol 1051®
SeaNine®
Zink omedin®
Copper
Estimated release to the marine environment
(kg)
200 – 14001
850 – 17002
11-222
not available3
not available3
16500 – 33 0002
Comment
At state of introduction
Table 9. Estimated amounts of antifouling biocides released to the marine environment round Denmark 1997.
1
data from DK EPA (1997) where TBT is given as Sn, 2DK EPA (1998) only from pleasure crafts, 3not available due to market confidentiality
(less than three manufacturers responded), at present both products are new to the market.
Danish regulatory practices for admission and usage of antifouling agents
At present, there is a regulation, as in most IMO memberstates, on antifouling use from 1991 when TBT was restricted for use
only on ships larger than 25 meters. Shortly, another regulation is due, concerning antifouling paints for pleasure craft, but it is not
approved by parliament at present. The main purpose is the banning of all toxic compounds used for pleasure craft, and is based
on Irgarol and Diuron environmental surveys in and around a pleasure-boat marina near Århus, Denmark. The draft regulation
was a total ban for any toxic compound used in antifoling paints. This caused uproar among pleasure boat owners who claimed
that no serious alternatives were available at present. Another draft of the regulation was issued proposing a stepwise phase out of
Irgarol and Diuron by the Year 2001. In addition, this should leave time for the manufacturers to implement and develop new
products.
In conjunction with the legislative work, a project rendering cleaner technology for antifouling techniques for pleasure boats is
currently being completed. The participants were VKI and J.C. Hempel A/S. NERI has participated in the steering committee for
expertise on TBT and antifouling in general. This project was, in brief, investigations of non-toxic alternatives for pleasure boats
using silicone or epoxy based antifouling paints supposedly preventing settling due to material properties. The silicone-based
material showed the most promising results, but none of these techniques showed satisfactory results.
DK EPA (1997): Massestrømsanalyse for tin med særlig fokus på organotinforbindelser, Arbejdsrapport fra Miljøstyrelsen Nr. 7 (1997), 132 p (In Danish)
DK EPA (1998): Kortlægning og vurdering af antibegroningsmidler til lystbåde i Danmark, ISBN: 87-7810-941-8 Miljøprojekt Nr. 384, Miljøstyrelsen, Copenhagen, Denmark (1998) 108 p (in
Danish).
15
Partner 8 - France
Methodology used:
The study of paint sales on a national scale was carried out directly with the manufacturers of antifouling paints. These
manufacturers were identified by consulting the various syndicates whose member firms have a paint-related activity. These
syndicates are grouped within the FIPEC (Fédération des Industries des Peintures, Encres, Couleurs, Colles et Adhésifs =
Federation of Industries for Paints, Inks, Dyes, Glues and Adhesives). Around 20 firms conducting activity within France were
identified and contacted. A parallel study was carried out with several local distributors (about 15) along the three maritime coasts
(English Channel, Atlantic Ocean, Mediterranean Sea) to ensure the good representativeness of the manufacturers consulted.
The study conducted with paint manufacturers concerned the following points:
- the quantities of antifouling paints produced for sale in France during one year (1998),
- the nature and quantities of biocide type (active substances) used in paint formulations. The specifications for the formulation
of the paints were obtained, which indicated the proportions of biocides used for each type of paint.
Results
For reasons of confidentiality at the request of the manufacturers, the results were compiled per active substance used without
indicating the names of the brands or manufacturers. The results presented concern sales in France for the year 1998.
Fourteen firms out of the 20 contacted participated in our study, and six provided sales figures. Contacts were made with local
sellers (some 15 distributors were consulted) to determine the manufacturers of the paint products they sold and confirm the good
representativeness of the information obtained from manufacturers.
The overall results indicated that around 190,000 liters (230 metric tons) of antifouling paints were sold in France in 1998. Three
manufacturers accounted for more than 90% of these sales (51%, 32% and 12% respectively).
The biocides used were mainly diuron, zinc pyrithione, chlorothalonil, dichlofluanid and Irgarol 1051, but also kathon 5287
(SeaNine 211) and zineb were used in quite negligible proportions. These biocides were used in association with copper oxide or
copper thiocyanate. The quantities sold in 1998 per active substance are indicated in Table 10. They were calculated as a function
of the annual amounts of paints sold by each manufacturer and of the mean composition of these paints. These figures represent
maximal estimations.
Active substances
Mean percentage used in paint
formulations
Quantities of biocides sold in
France
(kg/year)
Biocides sold
Copper oxide
50
99,200
79
Copper thiocyanate
25
9,600
8
Diuron
5
6,398
5
Zinc pyrithione
10
4,248
3
Chlorothalonil
5
3,600
3
Dichlofluanid
5
1,350
1
Irgarol 1051
5
891
1
TOTAL
---
125,287
100
(percentage of the total
amount)
Table 10: Quantities of pure active substances contained in antifouling paints
sold in one year (1998) in France.
16
1.2
An assessment of geographical patterns / differences in usage will be made.
Sub-task 1.2 – months 2-6
Title
Assessment of geographical patterns/differences in usage.
Responsible:
PML
Partners:
IVM, CSIC, UILIC, GU, VKI, NERI, IFREMER
Duration:
5 months
Objectives:
An assessment of geographical patterns/differences in usage.
Methods:
The information inputted to the database concerning usage etc. (see sub-task 1.1) will be investigated and
compiled to identify patterns/differences in usage within the countries represented within ACE. During the
inception workshop (workshop 1), tasks will be allocated to laboratories to obtain and compile
information on the usage of such products in other regions of the world, to identify potential inputs from
transient ships and potential future trends in usage.
Deliverables:
Input to database (sub-task 1.4) and major report 1 (sub-task 1.6).
Links:
1.1, 1.4, 1.5, 1.6, 2, 3, 4, 5
Summary
There are notable differences in usage patterns of booster biocides on pleasure boats throughout the European region.
The most commonly used biocides are: copper-oxide, Irgarol, diuron, dichlofluanid, and zinc pyrithione. In some
countries, recent regulations and voluntary agreements have caused a shift in the usage patterns, especially from
diuron and Irgarol to zinc pyrithione and SeaNine. For copper oxide, there are regulations on leaching rates and even
a ban has been proposed.
A survey on the antifouling biocides admitted in U.K showed that copper(1) oxide, diuron, Irgarol 1051 and zinc
pyrithion are the most used compounds. The survey in The Netherlands showed that 5 organic compounds are
currently registered for use as antifouling agents, i.e. diuron, Irgarol 1051, dichlofluanid, ziram and zineb. Copperoxide will possibly be banned totally in The Netherlands. Residues of antifouling compounds have been detected in
marine environments throughout Europe, sometimes where they are not permitted e.g. diuron was detected in
Swedish sea water where the usage of this compound is not permitted. In Denmark a new regulation was
implemented on January 1 2000, which includes a ban on Irgarol and diuron for boats < 25 m. In Denmark, from
2003 no booster biocides will be allowed unless they comply with the stringent safety and health risk assessment
marked R 53 (Risk of long term effects on the aquatic environment).
Geographical differences in the use of antifouling paints have been assessed indirectly by means of data for fishing
boats, ferry boats, tankers, pleasure craft in U.K., France, Spain, The Netherlands, Greece, Sweden and Denmark.
These data, obtained from various services belonging the Ministries of Mercantile Maritime, Equipment,
Transportation and Housing concerned the following:
- on a national level: the number of registered boats and the number of new registrations for a given year, as well as
the number of port facilities and installations for pleasure craft,
- on a regional level: the number of port facilities and installations for pleasure craft.
17
The objective of this sub-task is to identify the regions along the coasts of U.K., France, The Netherlands, Spain, Greece, Sweden
and Denmark, where contamination from antifouling products is most likely to occur. Possible geographical differences in the use
of antifouling paints were assessed indirectly by means of data for pleasure craft, fishing boats, ferry boats, tankers etc. in the
above mentioned European countries. Data were obtained from different national services belonging to the Ministries of Public
Works and Water management (U.K. and Netherlands), Mercantile Maritime (Greece), Equipment, Transportation and Housing
(France) concerning the following:
1)
2)
3)
4)
5)
Number of registered boats and the number of new registrations for a given year, as well as the number of port facilities and
installations for pleasure craft,
The number of port facilities and installations for pleasure craft.
Boating intensities on the National Continental Shelf
Counting of ship and boat traffic through sea ports and sea-going sluices and
Location of marina and yacht havens in the coastal areas. A distinction is made between shipping traffic which is
pleasurecraft related and shipping traffic which is related to commercial activities.
The data compiled by the individual partners follows:
Partner 1
U.K.
From the data collated by WRc, they estimated the quantities of antifouling biocides distributed/used in the UK/year (Table 11)
copper(1)oxide
copper thiocyanate
diuron
Irgarol 1051
zinc pyrithione
dichlofluanid
Maximum Amount (kg yr-1)
Minimum Amount (kg yr-1)
311769
4216
24738
10186
8246
388
75173
282
3288
59
1369
153
Table 11 . Antifouling biocides used per year in U.K.
Area
Number of vessels
Torbay
Milford Haven
Swansea
Bristol
North Wales
Lancashire
North Shields
Beaulieu
River Crouch
River Hamble
Southwold
The Wash
Southampton Water
1100
1200
12
500
400
600
400
110
2500
3261
180
300
2600
Table 12. Numbers of vessels in UK rivers and estuaries
18
Partner 2 The Netherlands
Dutch Continental Shelf / Nationaal Continentaal Plat (NCP).
The Dutch Continental Shelf (section of the North Sea) or the “Nationaal Continentaal Plat” (NCP), that comprises only 10 % of
the total area of the North Sea, contains by far the highest shipping intensities. Approximately 25 % of the total shipping traffic in
the North Sea is located in this area. On the NCP an average of 390 ship pass every day, i.e. 260,000 per year. The NCP is divided
into three sub areas, i.e. North, South and DW route (Figure 3). Table 13 gives an overview of the types of shipping traffic on the
NCP. A distinction is made between route bound and non-route bound traffic. Non-route bound traffic mainly consist of ships
used for fishery, recreation and working ships used for oil and gas production in the North Sea.
In Table 14 the division of shipping traffic to nationality on the NCP is given. This is important information if we consider the
fact that antifouling products may be admitted in a certain country while they are banned in, e.g., The Netherlands.
Ship type
Sub area
Carrying-trade
Tanker-trade
Bulk-trade
Container-trade
Passenger-ferries
Total
Number
South
97.2
28.9
15.2
8.6
2.6
DW-route
8.6
2.7
2.2
0.6
0.2
North
15.2
5.2
1.7
1.0
0.5
tot
120.9
36.8
19.1
10.2
3.3
%
tot %
31.3
9.5
4.9
2.6
0.9
ROUTE BOUND
Work-trade
Fishery
Recreation
Total
NON-ROUTE BOUND
152.5
29.6
85.4
8.8
14.2
2.9
19.6
0.4
23.6
6.3
42.7
0.7
190.3
38.8
147.6
9.8
49.2
10.0
38.2
2.5
123.8
22.9
49.6
196.3
50.8
276.3
37.1
73.2
386.6
100.0
Total
ALL
Table 13. Division of shipping traffic on the NCP to type and sub area (Netherlands)
Sea-going sluices
In order to gain information on the shipping intensities along the Dutch coast, counting of sluice passages were used as an
additional indication. Data on sluice passages were provided by the Ministery of Public Works and Water Management and only
data on sea-going sluices are presented (Table 15). From 1993 till 1997 the general trend is that an increasing number of pleasure
craft chose to sail in larger open waters. A decline is seen in 1998 which is attributed to bad weather conditions during the season.
nr.
1
2
3
4
5
6
7
8
Total
Location
Zeesluizen te Delftzijl
Robbengatsluis
Tsjerk Hiddessluis
Goereese sluis
Schutsluis Vlissinge
Roompotsluisn
Sluis te IJmuiden
Koopvaardersschutsluis
1993
5581
9858
9985
20767
19054
10680
9540
8811
94267
1994
4842
11545
10490
20014
20473
12357
10450
9546
99717
1995
4295
11803
11213
15545
21541
13877
13324
9463
101061
1996
5666
11899
12198
10403
17305
11450
11713
7890
88524
1997
6293
12971
13414
13465
19383
13256
12793
12075
103650
1998
7842
9153
11319
10548
15641
11123
10697
7425
83749
Table 15. Counting of pleasurecraft passages in sea-going sluices.
Marinas and yachting marinas
To assess the distribution of yacht havens in the Dutch coastal area, information was obtained from the Dutch association in the
water recreation branch (HISWA). With respect to the number of birthing places, no aggregated data are available for the Dutch
yacht havens. In Table 16 an overview is given of the numbers of yacht havens along the Dutch Coast. Data were obtained from
the Dutch branch organisation on water recreation (HISWA) and tourist brochures. For the Delta-area, detailed information was
available on the number of birthing places in individual yacht havens. Aggregated data is shown for waters which are either
19
directly connected to the North Sea or indirectly through sluices. A graphic presentation of the distribution of yacht havens along
the coast is depicted in Figure 5. From this figure it is clear that the Nieuwe waterweg, i.e. the entrance to the Rotterdam Harbour,
contains a relatively high number of yacht havens, next to the high shipping traffic due to commercial activities.
Country/flag
% verkeer Country/flag
%
Netherlands
37.1 Sweden
1.8
Germany
14.6 Poland
1.5
Denmark
14.6
4.9 USA
1.4
Russian Federation
4.8 France
0.9
Panama
3.3 Finland
0.8
Norway
3.0 Spain
0.8
Belgium
2.6 Japan
0.6
Cyprus
2.3 China / Hong Kong
0.5
Liberia
2.2 Saudi Arabia
0.5
Greece
2.0 Other
6.5
Table 14. Nationality of shipping traffic using the
NCP
Figure 3 : Sub-division of NCP into three areas.
Figure 4 A and B present the shipping intensities on the NCP for route bound and non-route bound traffic. For the route bound
shipping traffic, the shipping routes along the NCP are clearly identified (areas in black; > 45 ships per 1000 km2). For the nonroute bound traffic, which includes the pleasure craft, high intensities are found around IJmuiden, Noordwijk, Katwijk and
Walcheren (areas in red; 27-45 ships per 1000 km2).
A
B
Figure 4 Shipping intensities on the NCP. A) route bound and B) non-route bound shipping traffic
(Ministerie van Verkeer en Waterstaat, 1996).
20
Area
Delta
HISWA
yacht havens
13
25
8
10
54
12
2
1
5
8
1
1
1
5
3
2
1
2
1
21
Westerschelde
Oosterschelde
Grevelingenmeer
Veerse meer
Nieuwe waterweg
Haringvliet
Katwijk
Noordwijk
IJmuiden
Den Helder
Ameland
Den Oever
Delftzijl
Harlingen
Lauwersoog
Schiermonnikoog
Terschelling
Texel
Vlieland
Total
North Sea Coast
Wadden Sea
Tourist information
yacht havens
15
12
5
9
54
17
birthing places
2149
2358
2332
2126
6195
2693
650
4500
Table 16 : Density of yacht havens along the Dutch coast .
Ameland
Terschelling
Schiermonnikoog
Lauwersoog
Harlingen
Vlieland
Number of
yacht havens
Waddenzee
Delfzijl
Texel
1
2-5
Den Helder
6-10
Den Oever
11-25
IJselmeer
26-50
IJmuiden
51-
Katwijk
Nieuwe waterweg
Noordwijk
Haringvliet
Rotterdam
Grevelinge Meer
Eastern Scheldt
Veerse Meer
Western Scheldt
Figure 5: Density of yacht havens distributed along the Dutch coast.
21
Summary
A survey on the antifouling biocides admitted in the Netherlands showed that a number of 5 organic compounds are currently
registered for use as antifouling agents, i.e. diuron, Irgarol 1051, dichlofluanid, ziram and zineb. Figures on shipping traffic on the
NCP showed that less than 40% of the ships originate from the Netherlands. This indicates that a large part of the ships that visit
the harbours along the Dutch coast originate from other countries in which a different admittance policy might be conducted.
The results from a survey on the distribution of yacht havens, shipping intensities and sluice passages were combined to identify
the areas most relevant with regards to the contamination by antifouling agents. The following locations were selected; Harlingen,
Den Helder, IJmuiden, Katwijk, Hoek van Holland, Roompot sluis and Vlissingen. These locations will be monitored during a
period of at least one year (March 2000 till March 2001).
Partner 3 Spain
Copper based antifouling biocides with Irgarol , diuron and SeaNine are thought to be the most widely used on leisure craft in the
different marinas in Spain. Over the last year, an increase in the use of diuron, dichlofuanid and SeaNine has been observed
whereas the use of Irgarol has decreased.
Partner 4 Greece
The assessment of geographical patterns met difficulties as far as the collection of data is concern due to the lack of information
provided by relevant authorities. The places where the main boating activities take place, in Greece, are located nearby the ports
of Alexadroupolis, Kavala, Thessaloniki, Volos, Halkida, Pireaus, Eleusina, Patras, Ermoupolis (Syros-Neorio), Chania,
Kalamata, Preveza and Igoumenitsa. The main activities in these places are the application of antifouling compounds as well as
the removal of old paint from boat surfaces using sand particles (ammovoli).
Data were collected on the geographical distribution of Greek ports according to three categories: commercial ports, fishing ports
and marinas. These data obtained from the services of the Ministry of Mercantile Maritim. (Table 17).
Coasts
Alexadroupolis
Number of installations
3
Capacity
(berth number)
345
Kavala
4
459
Thessaloniki
12
1320
Volos
4
540
Halkida
5
623
Pireaus
15
1730
Eleusina
11
1240
Syros
2
120
Chania
3
465
Kalamata
6
534
Patras
3
340
Preveza
3
359
Igoumenitsa
4
235
Total
75
8,310
Table 17. Number of installations and their capacity (Greece).
The antifouling paints used in Greece are based on the following biocides, Irgarol 1051, copper (1)oxide, 4-m-chloro-cresol,
diuron, zinc pyritnione and dichlofluanid.
22
Thirteen sites in different places in Greece, including marinas, ports and shipping lines were selected for antifouling compound
monitoring in water, sediment and surface solid material from the work places.
The selected areas are:
-
Eleusina (Attici)
Marina (2 sampling stations)
-
Piraeus (Attici)
Marina, port and shipping line (3 sampling stations)
-
Halkida (Eyvia)
Marina, port and shipping line (3 sampling stations)
-
Thessaloniki-Kalamaria
Marina, port and shipping line (3 sampling stations)
-
Patras (Pelopponesus)
Port and shipping line (2 sampling stations)
-
Volos (Thessalia)
Port and shipping line (2 sampling stations)
-
Preveza-Aktio (Epirus)
Marina, Port and shipping line (3 sampling stations)
-
Igoumenitsa (Epirus)
Port and shipping line (2 sampling stations)
-
Syros-Ermoupolis (Syros)
Marina and port (2 sampling stations)
-
Chania (Creta isl.)
Port and shipping line(2 sampling stations)
Partner 5 Sweden
In 1997 the KEMI asked the local authorities to map the usage of antifouling paints in their district. Most local authorities have
chosen to check the sales and try to inform about the rules since the practical difficulties involved in actually controlling use of
antifouling paints were considered too big.
On the east coast south of Örskär observance of the rules are deemed good even though some west coast-quality paint are sold in
the southern Baltic sea area and there are suspicions of widespread missuse in some areas. North of Örskär the observance are
relatively good with few indications of misuse. In the freshwater lakes, especially in lakes with connection to the sea, use of east
coast-quality paints are considered relatively high.
Sales of westcoast-quality paint in the freshwater lakes and in the Baltic, north of Örskär are small and declared to be reserved for
boat owners with boats on the westcoast only.
Partner 6 &7 Denmark
The data (Table 18) concerning Denmark were based on:
a) Copper mass balance in DK
b) Organotin mass balance DK
c) Measurements in marinas in Aarhus County
d) Includeing airborne emmissions, wastewater treatment plants, riverine inputs.
e) Estimation based on 0.1-1% of argricultural use.
f) Estimation on organotin massbalance, not TBT-sn only.
Pleasure crafts
Larger vessels
Others sourcesd)
Total
Copper
Diuron
Irgarol
SeaNine
TBT-Sn
Others
16500-33000
18000-25000ª)
45000-63000ª)
100000
850-1700
Unknown
<7-70e)
2000
11-22c)
Unknown
0
Unknown
0
Unknown
0
Unknown
0
200-1400b)
<14f)
1400
150-300
Table 18. Input of antifouling agent to the marine environment in Denmark (kg/year) 1997
23
0
150
Partner 8 France
Data were collected on the geographical distribution of French ports according to three categories: commercial ports, fishing
ports, and pleasure craft harbours. For the last category, ports were classified in two subcategories according to the number of
berths available (between 500 et 1,000, and more than 1,000). Moreover, the study conducted with the French Ministry of
Equipment, Transportation and Housing allowed us to count the number of berths available for pleasure craft (162,331 in 466
installations). The number of boats registered on August 31, 1999, was 898,730, and the new registrations for the year 1998 were
18,595.
The figures for sales of paints were provided on a national scale without any distinction as to the regions receiving them.
However, several distributors indicated that their sales depended on the density of the port facilities. The study of the geographical
distribution of the number of berths reserved for pleasure craft in ports indicated that 55% of the 162,331 in France were located
on the Mediterranean coast, 9% on the North coast (English Channel), 20% in Brittany (English Channel and Atlantic Ocean), and
16% along the rest of the Atlantic coast (Table 19).
Number of installations
45
Capacity
(berth number)
15,095
Percentage of total
capacity
9.3
Brittany
164
33,120
20.4
Atlantic Ocean
73
25,794
15.9
Mediterranean Sea
184
88,322
54.4
Total
466
162,331
100.0
Coasts
North
Table 19. Geographical distribution of berth numbers in ports (France).
1.3 A survey and critical assessment of the environmental and toxicological properties will be compiled.
Sub-task 1.3 – months 2-6
Title
Survey and critical assessment of the environmental and toxicological properties.
Responsible:
GU
Partners:
VKI, NERI, IFREMER
Duration:
5 months
Objectives:
A survey and critical assessment of the environmental and toxicological properties.
Methods:
For all antifouling agents, information on environmental and toxicological properties will be assembled
(e.g. stability, partitioning coefficients, NOEC levels). The data obtained will be screened as regards their
quality according to the criteria agreed upon during the inception workshop (workshop 1). Data meeting
these criteria will be identified and included in the database to be set up (vide infra).
Deliverables:
Input to database (sub-task 1.4) and major report 1 (sub-task 1.6).
Links:
1.1, 1.2, 1.4, 1.5, 1.6, 2, 3, 4, 5
A literature survey on potential ACE compounds has been made and is included below. Focus is on
ecotoxicological effects in the marine environment and on biochemical mode of action. The
ecotoxicological information in the open literature is scarce on most compounds.
24
SURVEY AND CRITICAL ASSESSMENT OF ENVIRONMENTAL PROPERTIES
The survey of environmental propeties of a selection of alternative antifouling booster biocides, was initiated to provide input to
the Antifouling Data Base (Task 1.4) and to serve as a basis for selection of compounds for ACE to focus the experimental work
on.
Much of the relevant information was found in manufacturer´s reports cited by environmental authorities in their own
surveys/evaluations. When compiling such surveys the same information seem to appear over and over again. The list of reported
toxicity values therefor overestimates the actual amount of (original) information.
For some compounds very little information is found in the open literature. This makes our evaluation of the quality of data
difficult since we do not always have access to the original report.
The compilation is not yet fully completed, and the data base will most likely continue to grow throughout the ACE project.
However, for most substances sufficient information is available to get a rough idea of their basic environmental properties.
So far, only a very preliminary evaluation of the compiled data has been made. Also this work is likely to continue throughout the
ACE project as new information emerge, and is added to the Antifouling Data Base.
Procedures for classifying the quality of data, will be required before entering the information into the data base.
Tentative evaluation of compiled information
Ecotoxicity and biochemical mode of action
A summary of the ecotoxicity information available so far is given for a selection of antifouling agents in Table 20.
Chlorothalonil
Chlorothalonil binds to substances containing thiol groups. It is believed that chlorothalonil exerts its fungicidal toxicity by
inhibiting thiol-containing enzymes. In landliving mammals it seems primarily to cause damage to the proximal tubuli of the
kidneys and tumours in the kidneys and stomach. Also the compound causes allergy and is highly irritant to the eyes and skin.
The toxicity of chlorothalonil to aquatic fauna is rather well studied with a wide range of fish and invertebrate species
represented (e.g. Litchfield 1996). The aquatic toxicity is high with LC50 values for various fish species down to about 10 g/l.
Only one record of microbial toxicity is recorded, indicating algal toxicity to be low, with an EC50 for the diatom Amphora
coffaeformis of 2 mg/l (Callow & Willingham 1996).
Dichlofluanid
No information on the mode of action of the fungicide dichlofluanid is recorded in the compilation. The aquatic toxicity is
documented in only a few studies, suggesting acute toxicity to aquatic organisms (fish, Daphnia, algae) to be in the range of 0.031.0 mg/l.
TCMTB
TCMTB is a slimicide and fungicide used as wood preservative. It is toxic to aquatic invertebrates and fish (Wenell 1994), with
the lowest recorded effect concentration of 1.3 g/l for Daphnia. Algal toxicity is lower with EC50 of 0.1-0.3 mg/l.
Zineb
Zineb is a fungicide with a broad spectrum effect. It has been largely used earlier but at this moment there are no approved
products in Sweden. Zineb is an ethylenebisdithiocarbamate which in contrast to other dithiocarbamates form ethylenethiourea,
which has been shown to create tumours in mice and rats, on degradation and in the metabolism of plants and mammals. It is
believed that it is this and other degradation products that gives the toxic effect, probably by reacting with SH-groups of proteins.
Since most dithiocarbamates have the ability to form chelates with metals this might contribute to the fungicidal effect of
ethylenebisdithiocarbamates by blocking the metal group of the enzymes.
No information on aquatic toxicity is recorded in the compilation.
25
Table 20. Physiocochemical properties, persistence and toxicity of antifouling biocides
Biocide
Solubility
(mg 1-1)
Kow
Irgarol
2.2-11.1
631
diuron
42
Dichlofluanid
1.3
Copper(1)oxide
<0.007
Copper(1)thiocyanate
5
Koc
Degradability
Toxicity to fish
Toxicity to
algae
Reported
environmental
concentrations
Ref
1240 –
3100
Photolysis half life = 273
d; not readily
biodegradable
96 h LC50 for Zebra
Fish = 400 μg 1-1; 96
h LC50 Bluebell
sunfish = 2900 μg 1-1
72 h EC50
= 1.4 – 2.4
μg 1-1
4 – 130 ng 1-1
1
631
398
Limited photolysis; non
biodegradable
Bluegill 96 h LC50
8.5 – 25 mg/l
96 h EC50
0.04 – 0.12
mg/l
13 – 1000 ng 1-1
2
5000
1100
Bluegill sunfish =
0.03 mg/l
EC50 = 16
mg 1-1
10 – 10 200 μg 1-1
(Cu2+)
1 – 8000
μg 1-1
(Cu2+)
Median of approx.
7 μg 1-1 (Cu2+) for
estuaries used by
commercial and
leisure craft
4
10 – 10 200 μg 1-1
(Cu2+)
1 – 8000
μg 1-1
(Cu2+)
Median of approx.
7 μg 1-1 (Cu2+) for
estuaries used by
commercial and
leisure craft
4
zinc pyrithione
0.5
1
data provided by Ciba specialities
2
Lewis and Gardiner, 1996
3
Tomlin, 1997
4
ACP, 1998
LC50 50% lethality concentration
EC50 50% effect concentration
26
3
Irgarol 1051
Irgarol is a photosystem II inhibitor with affinity for the D1 protein in PSII. It is commonly used as an additive antifoulant with
copper in antifouling boat paints. It is extremely toxic to aquatic plants with effect thresholds as low as about 20 ng/l for marine
periphyton (Dahl & Blanck 1996). Also macroalgal reproduction-related processes is affected at low concentrations (160 ng/l for
germination of bladderwrack zygotes, Andersson 199x). Also vascular plants from the marione environment (Zostera marina) is
shown to be affected at 200 ng/l (Scarlett et al 1999).
Irgarol 1051 is obviously less toxic to non-photosynthesising organisms. The lowest recorded effect levels for fish is 4-9 g/l.
This is still considerably toxic.
A probabilistic risk assessment for Irgarol 1051 has recently been published (Hall et al 1999).
SeaNine 211
SeaNine 211 is an antifouling agent said to affect several enzymes in the Krebs’ cycle of microbial organisms. The fact that it is
affecting several enzymes reduces the possibility of tolerance mechanisms due to mutations of enzymes.
SeaNine is extremely toxic to marine microbial communities as recently shown by the preliminary data of the ACE project
(Blanck et al, Gustafson et al). It is also documented to have a high toxicity towards aquatic fauna in the range of 0.6-12 g/l ,
with Daphnia as the most sensitive animal. Single species algal tests indicate effects from about 13 g/l .
The suggested rapid degradation of SeaNine is presently under debate due to new ACE findings: its presence in the natural
environment and fairly slow disappearance from a natural marine water system with bacterial activity (Gustafson et al).
Diuron
to be completed
Zinc pyrithione
to be completed
1.4 A concise database with the information obtained will be developed.
Sub-task 1.4 – months 5-9
Title
The development of a concise database with the information obtained
Responsible:
PML
Partners:
IVM, CSIC, UILIC, GU, VKI, NERI, IFREMER
Duration:
5 months
Objectives:
To develop a concise database with the information obtained in sub-tasks 1.1, 1.2 and 1.3.
Methods:
The database will contain the information on the antifouling agents obtained, i.e. statistics on usage in
different regions, leaching rates, environmental and toxicological properties. (Full details of the database
and data management are provided in Section 5.2)
Deliverables:
Database and major report 1 (sub-task 1.6).
Links:
All tasks.
A concise relational database, built in Microsoft Access 97, has been constructed and will be made
available through the web. Data structures have been normalised to remove redundancy in tables and
formats for inputting data have been agreed by the partners.
27
During discussions at the First Annual Meeting, it was agreed that the inputting of data would be a shared
responsibility between partners. It was also agreed that the most important area to concentrate efforts
would be on the environmental/analytical data generated by the ACE Programme. The importance of
quality assurance was also discussed.

1.5 Literature on analytical techniques used for the different antifouling agents will be screened.
Sub-task 1.5 – months 2-9
Title
Screening of literature on analytical techniques used for the different antifouling agents.
Responsible:
CSIC
Partners:
UILIC
Duration:
8 months
Objectives:
To screen the literature on analytical techniques used for the different antifouling agents.
Methods:
A review will be made of analytical strategies for samples and information will be compiled on the
concentrations of antifouling agents in estuarine and marine waters. The results will be discussed in the
light of modern developments in analytical chemistry.
Deliverables:
Information generated to guide analyses of booster biocides. This information will be provided in major
report 1 (sub-task 1.6).
Links:
1.1, 1.4, 1.6, 2.1, 3, 4
Literature on analytical techniques has been screened by CSIC and ULIC. CSIC have compiled this
information and it is reported in three articles which have been submitted for publication (these are listed
under Sub-task 2.1).
ULIC’s screening of the literature on antifouling compounds revealed thirteen (13) papers on analytical
techniques and eleven (11) on monitoring. The papers were published in the Journals: Journal of
Chromatographogy (3), analytical chemistry (1), Environ. Sci. Technol. (6) Chemosphere (2), Water Air
and Soil Pollution (1), Water Research (2), Vibrational Spectroscopy (1), Marine Pollution Bulletin (4),
Crop. Protection (1), Sci. Total Environ. (1) and Applied Organometalic Chemistry (1).
Full details are provided below:
Analytical methods for antifouling pesticides
(a) using SPE (C18) followed by GC-MS
J.W. Readman et al., Environ. Sci. Technol., 27 (1993) 1940-1942
Gough A.M., Fothergill J. and Hendrie J.D. Marine Pollution Bulletin, 28, 10 (1994) 613-620.
S.Tóth, K.Becker-van Slooten, L. Spack, L.F. de Alencastro and J. Tarradellas, Bull. Environ. Contam. Toxicol., 57 (1996) 426433.
Tolosa, J.W. Readman, A Blaevoet., S.Ghilini, J. Bartocci and M. Horvat, Marine Pollution Bulletin, 32, 4 (1996) 426-433.
(b) using dichloromethane LLE followed by GC-MS
N. Voulvoulis, M.D. Scrimshaw, J.N. Lester, Chromatographia , 50, 5/6 (1999) 353-357.
D.Liu et alk., Water Research, 33 (1999) 2833-2843
(c) using ELISA (only for Irgarol)
I.Ferrer, B. Ballesteros , P. Marco and D. Barceló, Environ. Sci. Technol., 31 (1997) 3530-3535.
B. Ballesteros et al., Anal. Chim Acta, 347 (1997) 139-147.
28
B. Ballesteros et al., Anal. Chem., 70 (1998) 4004-4014
(d) using Immunosensor (only for Irgarol)
MA Gonzalez-martines et al., Envrion. Sci technol., 32 (1998) 3442-3447
(e) using SPE followed by LC-APCI-MS
K.V. Thomas, J. Chromatogr. A, 825 (1998) 29-35.
I.Ferrer and D. Barceló, J. Chromatogr. A, 854 (1999) 197-206
K. Thomas, J. Chromatogr.,A 825 (1998) 29-35
K. Martinez, I. Ferrer and D. Barceló, J. Chromatogra., A (in press)
(f) using SPME followed by GC-MS
A. Peñalver, E. Pocorull, F. Borrul and FM Marce, J. Chromatogr.,A 839 ( 1999) 253-260
(g) overview paper
N. Voulvoulis, M.D. Scrimshaw, J.N. Lester, Chemosphere , 38 (1999) 3503-3516

1.6 Information available will be assessed and antifouling agents on which studies will be focussed will be selected.
Sub-task 1.6 – months 8-10
Title
All available information relating to usage, transport, reactivity and toxicity will be assessed and final
choice of the antifouling agents on which the studies will be focused will be selected.
Responsible:
PML
Partners:
IVM, CSIC, UILIC, GU, VKI, NERI, IFREMER
Duration:
3 months
Objectives:
To assess all available information relating to usage, transport, reactivity and toxicity leading to the final
choice of the antifouling agents on which the studies will be focused.
Methods:
The information obtained will be discussed at Workshop 2 (see Table 1) with all partners. The different
antifouling agents will be discussed in the light of their volume of production and usage and
environmental properties (e.g. persistence and toxic properties). The potential for environmental
contamination / pollution will be assessed.
A strategy will be set out for the next phase of the project selecting compounds for further investigations
based on potential problems or, on the contrary, the expectation that the compounds will be a better
choice from the environmental point of view. Decisions will be made separately about the agents to be
included in a European Coastal Survey and the compounds for which persistence and toxic properties will
be assessed. This distinction is made as, at the present level of use, may not justify a survey to be
conducted, whereas an expert judgement may give rise to the conclusion that a formulation will (or
perhaps should be recommended to) be used in the future. The decisions will be made with the
perspectives and needs of the modelling in mind. The analytical chemistry requirements necessary in
order to undertake the survey will be established. The types of bioassays and semi-field studies will be
reviewed and agreed upon.
Deliverables:
Information providing final focussing of ACE (to be summarised in Major Report 1 (sub-task 1.6)).
Links:
1.1, 1.2, 1.3, 1.4, 1.5, 2, 3, 4, 5, Workshop 2
Following extensive discussions at the first Annual Workshop, booster biocides were selected for study in
the countries involved. Topics discussed included usage, transport, reactivity and toxicity, and availability
of analytical facilities.
29
The core group of compounds to be monitored within the ACE Programme was selected as:
Irgarol 1051
Dichlofluanid
Chlorothalonil
SeaNine
Diuron
Zinc pyrithione was also considered to be important even though the compound is difficult to analyse. It
was considered most feasible that sample analyses for this compound should be undertaken by those
partners best suited in terms of analytical facilities. The Danes, in collaboration with the Spanish partners
(and additionally zinc pryithione manufacturers -Arch Chemicals Incorporated), will investigate this
problem and will report back to the ACE Partners.
Toxicity tests will focus on Irgarol 1051 and SeaNine (it was considered that adequate data is already
available for diuron). Further long term and field toxicity tests will then focus on zinc pyrithione
(assuming appropriate analytical support is available).
Endocrine disruption experiments will focus on the core compounds and additionally on zinc pyrithione.

Task 2
Sub-tasks:
2.1
Develop analytical techniques and test models.
Suitably sensitive analytical techniques to measure environmental levels of selected “booster” biocides
will be developed. These will include IRGAROL 1051, 2,4,5,6-tetrachloroisophthalonitrile
(chlorothalonil), dichlorophenyl dimethyl urea (diuron), dichlofuanid and 4,5-dichloro-2-n-octyl-4isothiazolin-3-one (SeaNine 211). Techniques will be introduced within the participating analytical
chemistry laboratories where appropriate instrumentation is available. Performances will be
intercompared.
Sub-task 2.1.- months 3-12
Title
The development, testing and intercomparison of suitably sensitive analytical techniques
Responsible:
CSIC
Partners:
IVM , UILIC, PML, IFREMER
Duration:
10 months
Objectives:
To develop suitably sensitive analytical techniques (and to intercompare analyses) the to measure
environmental levels of compounds considered to be of concern.
Methods:
Analytical protocols will be developed for compounds that are considered to be of concern from initial
assessments of the literature, techniques for the following compounds will be developed: IRGAROL 1051,
2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil), dichlorophenyl dimethyl urea (diuron), dichlofuanid
and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (SeaNine 211). Techniques will be assigned to the
partners according to analytical capabilities and geographical relevance. Matrices for analyses will be
determined according to the predicted linear free energy distributions between environmental
compartments.
30
The analytical techniques developed will be distributed to the partner laboratories for further testing and
use. Where partner laboratories do not have the analytical capacity for quantifying all determinands,
samples will be provided to laboratories with the capabilities. For the other analyses, inter-laboratory
studies will be developed and run.
A rapid immunoassay protocol to measure IRGAROL 1051 will also be developed (Partner 3).
Deliverables:
The analytical protocols essential to investigate contamination, degradation and ecotoxicology.
Links:
1.4, 1.5, 1.6, 3.1, 3.2, 4, 5
CSIC have been prolific in the development of analytical techniques. Three papers have been submitted
for publication:
Imma Ferrer & Damià Barceló, Simultaneous determination of antifouling herbicides in marina water by
on-line sold-phase extraction followed by liquid chromatography-mass spectrometry. Journal of
Chromatography A, 854 (1999) 197-206
Montserrat Castillo and Damià Barceló. Identification of polar toxicants in industrial wastewaters using
toxicity-based fractionation with liquid chromatography/mass spectrometry. Analytical Chemistry,
Vol. 71, Number 17 (1999) 3769-3776
Karell Martinez, Imma Ferrer and Damià Barceló. Part-per-trillion level determination of antifouling
pesticides and their by-products in seawater samples by off-line sold Phase Extraction followed by
HPLC-APCI-MS.
Preliminary method development was performed by IVM for a set of selected antifouling agents. The
studies aimed at finding the most sensitive analytical technique, i.e. gas chromatography coupled to iontrap tandem mass spectrometry or liquid chromatography coupled to electrospray tandem mass
spectrometry.
UILIC have developed a multiresidual analytical method for analysis of 6 antifouling compounds Irgarol
1051, diuron, chlorothalonil, dichlofluanid, 4-chloro-meta-cresol and folpet in water and sediment samples
was developed. The method includes of SPE-disks and SPME-fibers for sample preparation followed by
GC-FTD and GC-ECD techniques. An analytical method for the determination of antifouling compounds
mancozeb, maneb thiram, zineb was also developed using UV-Vis spectroscopy.
PML have concentrated on the use of GC-MS to quantify Irgarol 1051, dichlofluanid and chlorothalonil.
The technique has been fully tested and applied to environmental samples. Research continues into
methods of diuron analyses.
IFREMER are testing XAD-2 extraction with capillary GC-NPD/ECD and MS quantification to quantify
Irgarol 1051, diuron, dichlofluanid and chlorothalonil. Work is on track.
Details concerning the performance of the analytical techniques selected by the partners are currently
being compiled for inclusion in the next annual report.
The only aspect of the ACE programme which is not on schedule is the inter-comparison exercise within
the Sub-task. This was postponed awaiting the outcome of discussions relating to selection of compounds
to monitor (see Sub-task 1.6). This will now go ahead.

31
2.2
Models capable of predicting concentrations and effects in coastal situations (for different scenarios of
usage) will be assessed and developed
Sub-task 2.2 – months 9-30
Title
Implementation of models capable of predicting concentrations and effects for different scenarios.
Responsible:
IVM
Partners:
PML
Duration:
21 months
Objectives:
Implementation of models capable of predicting transport, reactivity, concentrations and effects in model
situations for different scenario’s for usage (utilising the most effective models available from EXAMS II,
Delwag/Charon, EQC and Jackson0Baar Modd)
Methods:
Two of the partners within this project (IVM and PML) currently have proven models which, with
adjustment, are admirably suited to address this sub-task. A study (financed by the European Paintmakers
Association CEPE) is presently being carried out at IVM to compare and evaluate a number of existing
computer models for the prediction of antifoulant levels in the aquatic environment. Among the models
currently available are: ECOS (Plymouth Marine Laboratory), EXAMS II (US-EPA), Delwaq/Charon
(Delft Hydraulics), EQC (Environmental Modelling Centre Canada) and the Jacobson-Bauer model
(Rohm & Haas company). Based on the outcome an improved model will be developed at Delft
Hydraulics; its completion is scheduled for Autumn 1998. The results will be used during the course of
this project.
Deliverables:
An evaluation of models to predict the environmental behaviour of biocides (major report 3).
Links:
1.4, 1.6, 3, 4, 5
Work within this Sub-task has now commenced and is on-track.

Task 3
Environmental chemical surveys and experiments.
Sub-task 3.1.- months 7-30
Title
Assessment of the extent of contamination of European coastlines through chemical surveys of relevant
areas
Responsible:
PML
Partners:
IVM , UILIC, IFREMER, CSIC, GU. VKI, NERI
Duration:
23 months
Objectives:
To assess the extent of antifouling agent contamination of European coastlines.
Methods:
Once installed and tested, analyses will commence on environmental samples for the antifouling agents
listed in Subtask 2.1. Areas previously identified as those potentially subject to most contamination will be
targeted for assessment. ‘Good geographical coverage’ will also, however, be incorporated as a
prerequisite in survey design. A critical feature relating to the potential for pollution by antifouling agents
is the dissipation of the compounds from marinas and harbours. It is accepted that toxic concentrations
are likely to exist in the direct proximity to the vessels, and the primary concern is that coastal
environments adjacent to port facilities will be impacted (as was the case for TBT). As part of the surveys
undertaken, intensive investigations will be performed at the most contaminated locations to investigate
dissipation.
32
Samples will be exchanged between partners in order to ensure that a full data set is generated for each
area. The survey data produced by individual partners will be compiled to provide a Europe-wide
assessment of coastal contamination with the antifouling agents in question.
Deliverables:
Maps depicting the extent of contamination of European coastlines by the selected booster biocides.
Links:
1.4,1.6, 2.1, 2.2, 4, 5
Field validations of the selected analytical techniques have been undertaken and coastal surveys have
commenced. Locations have been selected from the information compiled in sub-tasks 1.1 and 1.2.
Task 4
Sub-tasks:
4.1
Conduct ecotoxicological investigations.
Develop bioassays to investigate toxic effects for IRGAROL 1051, SeaNine 211 and diuron.
Sub-task 4.1 – months 3-20
Title
Bioassays to investigate toxic effects of the selected antifouling agents
Responsible:
GU
Partners:
VKI, NERI, PML
Duration:
18 months
Objectives:
Effects studies (bioassays) to investigate toxic effects.
Methods:
Bioassays to be conducted on IRGAROL 1051 and SeaNine 211. These will include:

Short-term toxicity of antifouling agents to microbial activity in periphyton and plankton.

Experimental ecosystem studies of effects on microbial communities of antifouling agents
Ecosystem studies of effects on microbial communities by antifouling agents (TBT, Irgarol 1051, SeaNine
211) around selected harbours.
Deliverables:
An assessment of the toxicity of the “most-used” biocides. These results will form the basis of major
report 6.
Links:
1.3, 1.4, 1.6, 2.2, 3.1, 3.2, 4.3, 5
A microcosm study of SeaNine 211 focusing on marine periphyton communities was made during
summer 1999, partly in co-operation with the PREDICT project. Preliminary analysis of the results
suggest effects in the low nanomolar range. Further evaluation of the results are in progress and a
manuscript is in preparation. (GU).
A field study of Irgarol 1051 effects on periphyton communities was performed in the Fiskebäckskil area
on the Swedish west coast during summer 1999. Effects were estimated according to the PICT concept, by
measuring community tolerance to Irgarol 1051. Two different methods were used to measure the
tolerance of periphyton: incorporation of radiolabelled carbon dioxide and variable in vivo fluorescence
(PAM). A community tolerance (PICT) was observed close to the marina which was the anticipated major
Irgarol source. The PAM was unable to detect this PICT signal. (GU)
The observed community tolerance was stronger than observed in a previous study (Blanck & Dahl 1994,
unpublished) and the reason for this is now being evaluated. The collaboration with the Barcelona group
for analysis of Irgarol in Swedish waters, will reveal wheteher Irgarol exposure has increased since 1994
33
or whether Irgarol tolerance in periphyton takes several years to develop. The evaluation of the new data
will be made during spring 2000. (GU)
Effect of SeaNine on natural phytoplankton communities from coastal water was investigated in
microcosms experiments. SeaNine was added once at start of the experiment. Distinct effect of SeaNine
on photosynthetic activity, community tolerance (PICT) and species composition was seen. Preliminary
analysis of the results indicates effect in nanomolar range. However the biological activity in the eutrophic
water was very high the half-live for SeaNine in the experiment was about 3 days and effect of SeaNine
still persist still after 15 days. (VKI)
In another microcosm experiment, bacterial degradation of SeaNine was investigated. Chemical analysis
indicated very slow degradation of SeaNine and the bioassays were toxicity of the water were tested on
natural phytoplankton communities indicate a persist of the toxicity. In microcosms added 100 nM the
toxicity persists until 28 days. At lower addition of SeaNine 32 and 10 nM the toxicity persist one week.
Bacterial activity was at the beginning of the experiment two days after the GF/C filtration realistic for
coastal water. Initial the bacterial activity decrease after the addition of SeaNine however, a full recovery
was seen after few days. Preliminary analysis of the results indicates slow degradation of SeaNine in
coastal water without phytoplankton and in dark. Results of the experiment will be submitted for
publication in 2000. (VKI)
PML have developed toxicological techniques using flow cymtometry and pigment analyses to assess the
affect of Irgarol 1051 on natural phytoplankton populations. This work is being compiled for publication.

Annual Workshops
Subsequent meetings/workshops will be organised (in order to plan development of databases, analytical methodologies, surveys,
experiments and models, etc., and to agree the design of the programme) on an annual basis. All workshops will be co-ordinated
by the Project Co-ordinator. Following completion, results from the development of methods and models and of the
measurements/experiments will be discussed and integrated within these fora.
The first annual workshop to discuss results achieved during the first year of the ACE programme was
held on 3 and 4 February 2000 in Barcelona, Spain. Full details are provided in the Workshop Report
attached as Annex II.

Initiatives for the dissemination of results
An ACE web site has been set up at www.pml.ac.uk/ace.

34
References
Anderson, C.D. (1993). Self polishing antifoulings: a scientific perspective. Courtaulds Coating, International Pain, Newcastle.
Baart, A. and J. Boon (1998). Scremotox: A screening model for comparative ecotoxicological risk-assessment of substances entering the North
Sea. Delft HydraulicsWL, Delft.
Baur, D., A. Jacobson (1996). Modelling of marine antifoulants. Rohm and Haas Company, European Laboratories, Valbonne (France) and
Research Laboratories, Spring House (PA, USA), p. 1-12 (manuscript).
Belfroid, A.C., A.G.M van Hattum en J.H.N. Meerman (1999). Detectie van oestrogeen-actieve stoffen met in vitro bioassays. STOWA rapport
99/18, Utrecht.
Berg, E.A. (1995). Measuring copper release from antifouling paints. EJC 7-8/95, p. 534-538.
Bockting, G.J.M., E.J. van de Plassche, J. Struijs and J.H. Canton (1993). Soil-water partition coefficients for organic compounds. RIVM Report
no. 679101013, p. 46.
CEPE-AWG (1998). Classes of biocidal antifouling paint commercially available in the European Union. CEPE, Brussels.
Ciba (1995). Summary on ecological and health effects of Irgarol 1051. Information Brochure Ciba Geigy 5/1/1995.
Cooper, H., J. William and F.L. Frank (1987). Photochemistry of environmental aquatic systems. ACS Symposium Series 327. American Chemical
Society, Washington DC.
Cowan, C.E., D. Mackay, T.C.J. Feijtel. D. van de Meent, A. Di Guardo, J. Davies and N. Mackay (1995). The multi-media fate model: a vital
tool for predicting the fate of chemicals. SETAC Press, Pensacola (Fl).
CTB, (1999), http://www.bib.wau.nl/ctb/
Cutland et al. (1987). Cost 301 Final Report. EC-Cost 301/FRZ.00 [AN 0102], EASAMS, UK.
Dahl, B. and H. Blanck (1996). Mar. Pollut. Bull., 32, p. 342-350.
De Rooij, N.M. (1991). Mathematical simulation of biochemical processes in natural waters by the model Charon. Documentation report T68,
WL|Delft Hydraulics, Delft.
DELFT HYDRAULICS (1993). IMPAQT 4.00: User's Manual (H.L.A. Sonneveldt, J.G.C. Smits, G.A.J. Mol and R. van der Hout).
DELFT HYDRAULICS (1994). DELWAQ 4.0: Technical Reference Manual (P.M.A. Boderie; draft).
DELFT HYDRAULICS (1995). AQUAPOL, Chemical Database (version 1.01). Manual.
DELFT HYDRAULICS (1997). Modelling Suspended of Suspended Particulate Matter (SPM) in the North Sea Z2025 (J.G. Boon, v.d. Kaaij, Vos
and Gerritsen).
ECB (1997). EUSES - The European union system for the evaluation of substances. Joint Research Centre European Commission Environment
Institute, European Chemicals Bureau, Ispra (Italy).
Evers, E.H.G., J.H. van meerendonk, R. Ritsema, J. Pijnenburg en J.M. Lourens (1995). Watersysteemverkenningen 1996. Butyltinverbindingen een analyse van de problematiek in aquatisch milieu. Rapport RIKS-95.007. Rijksinstituut voor Kust en Zee, Den Haag.
Fairplay (1997). Fairplay Ports Guide 1997. Volume 1-IV. Fairplay Publications Ltd., London.
Fent, K. (1996). Ecotoxicology of organotin compounds. Crit. Rev. Toxicol. 26, 1-117.
Halfon, E. and R.J. Allan (1995). Modelling the fate of PCBs and Mirex in aquatic ecosystems using the TOXFATE model. Environmental
International 21, p. 557-569.
Hare, C.H. (1993). Anatomy of paint - antifouling coatings. J. Protective coatings and linings, Vol. 10, 83-90.
Harris, J.R.W., R.N. Gorley, C.A. Bartlett (1993). ECOS version 2 user manual - an estuarine simulation shell. Plymouth Marine Laboratory,
Plymouth, UK.
Harris, J.R.W., R.N. Gorley, C.A. Bartlett (1993). ECOS version 2 user manual - an estuarine simulation shell. Plymouth Marine Laboratory,
Plymouth, UK.
Hattum, B. van, A.C. Baart, J.G. Boon, R.J.C.A. Steen and F.Ariese (1999). Computer model to generate predicted environmental concentrations
(PECs) for antifouling products in the marine environment. IVM-E99/15, Institute for Environmental Studies, Amsterdam, 68 p.
HISWA, (1999), http://www.hiswa.nl
Howard, P.H. and W.M,. Meylan (1997). Prediction of physical properties, transport, and degradation for environmental fate and exposure
assessments. In: Chen, F. and G. Schüürmann, (Eds.), Quantitative structure-activity relationships in environmental sciences – VII. SETAC
Press, Pensacola (Fl).
Jausons-Loffreda N, Balaguer P, Roux S, Fuentes M, Pons M, Nicolas JC, Gelmini S, Pazzagli M, 1994. Chimeric receptors as a tool for
luminescent measurement of biological activities of steroid hormones. J. Biolumin. Chemilumin. 9:217-221
Johnson, A., R. Luttik (1994). Risk assessment of antifoulants - position paper. Paper nr. 1994-05-03. Paper presented at the 7th meeting of the Ad
Hoc Group of Experts of Non-Agricultural Pesticides, 16-18 May 1994. National Chemicals Inspectorate, Sweden; National Institute for
Public Health and the Environment, Netherlands.
Karman, C.C, E.A. Vik, H.P.M. Schobben, G.D.Øfjord and H.P. van Dokkum (1996). Charm III Main Report. TNO-MEP R 96/355. Institute of
Environmental Sciences, Energy Research and Process Innovation (TNO-MEP), Department of Ecological Risk Studies, Den Helder
(Netherlands).
35
Legler J, van den Brink CE, Brouwer A, Murk AJ, van der Saag P, Vethaak AD, van der Burg B, 1999. Development of a stably transfected
estrogen receptor-mediated luciferase reporter gene assay in the human T47D breast cancer cell line. Toxicol. Sci. 48:55-66
Lindgren, P., B. Olsson, and C. Unger (1998). Antifoulingsprodukter FARTYG. PM-beslut 1998-10-20. KEMI, Stockholm (Sweden).
Ling, H., M. Diamond, D. Mackay (1993). Application of the QWASI fugacity/equivalence model to assessing sources and fate of contaminants
in Hamilton Harbour. J. Great Lakes Research 19, p. 582-602
Ling, H., M. Diamond, D. Mackay (1993). Application of the QWASI fugacity/equivalence model to assessing sources and fate of contaminants
in Hamilton Harbour. J. Great Lakes Research 19, p. 582-602
Mackay D. W.Y. Shiu, K.C. Ma (1997). Illustrated handbook of physical-chemical properties of environmental fate for organic chemicals.
Springer-Verlag, Berlin/Heidelberg.
Mackay, D. (1991). Multimedia Environmental models. The fugacity apporach. Lewis Publishers Inc., Chelsea Michigan.
Mackay, D. et al. (1996). Assessment of chemical fate in the environment using evaluative, regional and local scale models: illustrative
application to chlorobenzene and linear alkylbenzene sulfonates. Environ. Toxicol. Chem. 15, p. 1638-1648.
Makela S, Davis V, Tally WC, Korkman H, Salo L, Santti R, Vihko R, Karoach KS, 1994. Dietary estrogens act through receptor mediated
processes and show no antiestrogenicity in cultured breast cells. Environ. Health Perspect. 102:572-578
Matthiessen P. & J. Reed (1997). Evaluation of copper and zinc concentrations in Suffolk and Essex estuaries. CEFAS report C967E280.
Miller, G.J. (1982). Ecotoxicology of petroleum hydrocarbons in the marine environment. In: Journal of Applied Toxicology, Vol. 2, No.2,
Heyden & Son Ltd, Great Britain, p. 88-98.
Ministerie van Verkeer en Waterstaat, (1996), Voortgangsnota Scheepvaartverkeer Noordzee – 1996 "Recht-zo-die-gaat", Directoraat-Generaal
Goederenvervoer, directie Transportveiligheid afdeling Verkeersmanagement, Den Haag, The Netherlands.
Ministerie van Verkeer en Waterstaat, (1998), Signaalpuntennet Recreatievaart, Directoraat-Generaal Rijkswaterstaat, Adviesdienst Verkeer en
Vervoer, Heerlen, The Netherlands.
Pons M, Gagne D, Nicolas JC, Mehtali M, 1990. A new cellular model of respose to estrogens: a bioluminescent test to characterize (anti)estrogen
molecules. Biotechniques 9: 450-459
Routledge, E.J. and J.P. Sumpter (1996). Estrogenic activity of surfactants and some of their degradation products assessed using a recombinant
yeast screen. Environ. Toxicol. Chem.,
Vol. 15, No. 3, p. 241-248.
Scarlett, A., M.E. Donkin,T.W. Fileman and P.Donkin (1997). Occurrence of the marine antifouling agent Irgarol 1051 within the Plymouth
Sound locality: implications for the green macroalga Enteromorpha intestinalis. Mar. Pollut.Bull 34, p. 645-651.
Schwartz J.A. and D.F. Skafar (1993). Ligand-mediated modulation of estrogen receptor conformation by estradiol analogs. Biochemistry, 32:
10109-10115
Severinsen, M., M.B. Anderson, F. Chen and N. Nyholm (1996). A regional chemical fate and exposure model suitable for Denmark and its
coastal sea. Chemosphere 32, 2159-2175.
Smeets, J.M.W. (1999). In vitro assays for effects of contaminants on fish. PhD thesis. Utrecht University, The Netherlands.
Soto AM, Lin T-,Justica H, Silvia RM, Sonnenschein C. 1992. An “in culture” bioassay to assess the estrogenicity of xenobiotics. In: ChemicallyInduced Alteration in Sexual Development: The Wildlife/Human Connection (Colburn T, Clement C, eds). Princeston, NJ: Princeston
scientific publishing, pp. 295-309.)
Steen, R.J.C.A., A.C. Hogenboom, P.E.G. Leonards, R.A.L. Peerboom, W.P. Cofino and U.A.Th. Brinkman, (1999), “Ultra-trace-level
determination of polar pesticides and their transformationproducts in surface and estuarine water samples using column liquid
chromatography-electrospray tandem mass spectrometry, J. Chromatog. A., 857, 157-166
Steen, R.J.C.A., P.E.G. Leonards, U.A.Th. Brinkman and W.P. Cofino, (1997), “Ultra-trace-level determination of of the antifouling agent Irgarol
1051 by gas chromatography with tandem mass spectrometric detection, J. Chromatog. A., 766, 153-158
Stronkhorst, J. (1996). TBT Contamination and toxicity of sediments: a persistent problem. In: Stewen, U. (ed.). The present status of TBTcopolyment antifouling paints. Proceeding of International One Day Sympoisum on antifouling paints for ocean-going vessels, 21st Febr.
1996, The Hague. Ministry of Transport, Public Works and Water Management, Rijkswaterstaat, DGSM; ORTEP, Association, The Hague,
Netherlands.
Thomas, K.V. (1998). Determination of selected antifouling booster biocides by high-performance liquid chromatography-atmospheric pressure
chemical ionisation mass spectrometry. J. Chromatography A 825, p. 29-35.
Trapp, S. and M. Matthies (1997). Chemodynamics and environmental modelling – an introduction. Springer Verlag, Berlin/ Heidelberg.
Willemsen and Ferrari (1992). Emissions of organotin to Dutch surface waters. TNO-Coatings, Den Helder (in Dutch).
Willingham, G.L. and A.H. Jacobson (1996). Designing an environmentally safe marine antifoulant. In: De Vito, S.C and R.L. Garrett (eds).
Designing safer chemicals - Green chemistry for pollutant prevention. American Chemical Society, Washington DC. ACS Symposium Series
640, p. 225-233.
WL (1995). Silthar - a mathematical programme. Delft Hydraulics, Delft.
WL (1996). Technical reference of the 3D-WAQ Model. Delft Hydraulics, Delft.
36