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Annex
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ACE
MAST-III PL971620
0. Abstract
Title: ASSESSMENT OF ANTIFOULING AGENTS IN COASTAL ENVIRONMENTS
Acronym: ACE
In 1989 the European Community introduced a directive to restrict the use of TBT-based
antifouling paints on boats under 25m. This, in combination with other National and
International legislation, has provoked paint manufacturers and chemical companies to
develop and vend a range of agents for new antifouling paints for the “small boat” market and
as an addition to TBT-based formulations to enhance efficacy for larger vessels.
Examples of the types of compounds being used or promoted include: 2,3,5,6-tetrachloro-4(methyl sulphonyl) pyridine; 2-methylthio-4-tertiary-butylamino-6-cyclopropylamino-s-triazine
(IRGAROL 1051); cuprous thiocyanate; 2,4,5,6-tetrachloro iso phthalo nitrile; 4,5-dichloro-2n-octyl-4-isothiazolin-3-one (SeaNine 211); dichlorophenyl dimethylurea (Diuron);
2(thiocyanomethyl thio)benzthiazole; zinc pyrithione; 4-chloro-meta-cresol; arsenic trioxide;
cis 1-(3-chloroallyl)-3,5,7-triaza-1-azonia adamantane chloride; zineb; dichlofluanid; folpet;
thiram; oxy tetracycline hydrochloride; ziram and maneb. This list includes compounds which
are known to be highly toxic (e.g. cyanides, arsenicals) or to act as endocrine disrupters (e.g.
maneb, ziram) but negligible data concerning contamination, (potential) effects and risks of
these compounds in the coastal and marine environment are available.
Data are currently not available concerning the usage, distribution and effects of most of
these biocides (IRGAROL 1051 being the only exception). Indeed, for most, suitably sensitive
analytical protocols are not available.
This project will redress this situation and through multidisciplinary research will provide:

Information on usage and geographical differences in usage of antifouling agents and
products in Europe.

Suitably sensitive analytical (chemical) techniques for quantifying antifouling “booster”
biocides.

An assessment of the extent of contamination of European harbours and marinas and
coastal waters through chemical surveys.

Information concerning the dissipation, transport and ecotoxicological effects of “booster”
biocides (through experimentation under laboratory and field conditions).

Models which predict environmental concentration and impact.

A critical comparison of products regarding environmental impact.
Results will provide essential information upon which National and International Authorities
and the Commission can consider and provide well-founded advice (and hence management
options) on the topic of antifouling agents.
2
1. Objectives and Methodology
The project will address the following objectives:

To survey antifouling agents and products being marketed within UK, NL, ES, GR, SE,
DK and FR. To direct analytical and experimental work towards relevant biocides, the
individual partners will investigate National manufacture, registration, importation and
localised usage of antifouling agents. In addition, details of boating activities/densities
within the countries will be recorded at monitoring sites for modelling purposes. This
information will be used to assess geographical patterns and differences in usage within
Europe.

To develop suitably sensitive analytical techniques to measure environmental levels.
‘State of the art’ gas and liquid chromatographic techniques will be used in the
quantification with relevant detectors including MS and MS/MS. Techniques are currently
available for IRGAROL 1051. Other compounds for which analytical techniques will be
produced will include: 2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil), dichlorophenyl
dimethyl urea (diuron), dichlofuanid and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one
(SeaNine 211). \the application of LC-MS to screen other booster biocides will also be
investigated. Immunoassays will also be developed for IRGAROL 1051.

Once installed and tested, analyses will commence on environmental samples. Areas
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). Analyses will be conducted for the compounds for
which techniques are developed (as listed in the above bullet point) and maps showing
contamination at a National and European scale will be generated. As part of the surveys
undertaken, intensive investigations will be performed at the most contaminated locations
to investigate dissipation, transport and fates.

Samples will be exchanged between partners in order to ensure that a full dataset is
generated for each area. Survey data produced by the individual partners will be compiled
to provide a Europe - wide assessment of coastal contamination by the alternative
antifouling agents in question.

To investigate fates and effects, laboratory studies will be run to assess the degree of
physical and chemical degradation of the antifouling agents. In the literature, few or
conflicting data are available regarding the persistence of antifouling agents. In this
project, a consistent set of degradation studies will be carried out so as to obtain reliable,
comparable information for compounds of interest.

Bioassays to investigate toxic effects will be conducted on the most relevant compounds
including IRGAROL 1051, SeaNine 211 and diuron. 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 (Sea-nine
211, Irgarol 1051); Ecosystem studies of effects on microbial communities by antifouling
agents (TBT, Irgarol 1051, Sea-nine 211) around selected harbours. Bioassay
experiments will also be used to investigate the endocrine disrupting characteristics of the
antifouling agents using a yeast screen assay and an estrogenic assay based on a
mammalian breast cancer celline.

The validity of predictions derived from the selected bioassay results will be tested under
semi-field conditions.

To model the behaviour of the compounds in coastal environments. A database
generated throughout the project will be used to provide the essential information
3
necessary to run currently available (well tested) estuarine/coastal models within 2 of the
partner institutions.

A final workshop will be held to collate data and information in preparation for the final
report. The key thrust of discussions will be to assess the potential impact from the
various antifouling agents and to recommend preventative measures and/or remedial /
advisory actions where necessary. To balance the efficacy of the products with potential
environmental impacts, major industrial manufacturers/distributors will be involved within
these discussions.
2. Task Structure of the Project
Whilst it is important that a multidisciplinary approach is retained to maximise outputs of the
project, to aid management, enhance efficiency and facilitate the definition of deliverables, the
project is divided into 5 major tasks each involving several sub-tasks. A summary of the
structure, responsibilities for the tasks, participants, milestones and timetables is provided in
Table 1.
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.
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.
1.2
An assessment of geographical patterns / differences in usage will be
made.
1.3
A survey and critical assessment of the environmental and toxicological
properties will be compiled.
1.4
A concise database with the information obtained will be developed.
1.5
Literature on analytical techniques used for the different antifouling agents
will be screened.
1.6
Information available will be assessed and antifouling agents on which the
studies will be focused will be selected.
Task 2
Develop analytical techniques and test models.
Sub-tasks:
2.1
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-noctyl-4-isothiazolin-3-one (SeaNine 211). Techniques will be introduced
within the participating analytical chemistry laboratories where appropriate
instrumentation is available. Performances will be intercompared.
2.2
Models capable of predicting concentrations and effects in coastal
situations (for different scenarios for usage) will be assessed and
developed.
4
Task 3
Conduct environmental Chemical surveys and experiments.
Sub-tasks:
3.1
Assessment of the extent of contamination of European coastlines through
analytical chemical surveys of relevant areas for the compounds listed in
Task 2.1. Maps indicating contamination of both National and European
scales will be produced.
3.2
Laboratory studies will be conducted to assess the degree of physical and
chemical degradation of the antifouling agents.
Task 4
Conduct ecotoxicological investigations.
Sub-tasks:
4.1
Develop bioassays to investigate toxic effects for IRGAROL 1051,
SeaNine 211 and diuron.
4.2
Develop bioassays to investigate the endocrine disrupting characteristics
of the antifouling agents.
4.3
Investigate whether effects observed under laboratory conditions occur
under (semi-) field conditions
Task 5
Integrate results and evaluate risks.
Sub-tasks:
5.1
Update/extend the database.
5.2
Use the database and models to predict concentration levels and effects in
selected European coastal zones using different scenario’s for usage
5.3
Undertake a critical comparison of the products selected regarding
environmental impact
Each task will result in at least one major project report.
An overview of the proposed workplan and schedule is provided in Table 1. MR1-MR8
represent major reports and FR the final report. The Table also shows which partners are
responsible (R) and which participate (P) in the sub-tasks.
3. Role of the Participants
Details of the role of each partner are given below. Tasks and sub-tasks are indicated simply
by their respective number in brackets and are summarised in Table 1. No sub-contractors
are proposed within the project.
Partner No. 1
Natural Environment Research Council, Centre for Coastal and
Marine Sciences, Plymouth Marine Laboratory (PML), Plymouth, UK.
Role:
In the programme, as indicated in Table 1, a primary role of the PML staff
will be to coordinate the project and responsibility is taken for ensuring
implementation of many of the sub-tasks and reporting. Scientists at PML
will also specifically contribute to the science by:

Surveying antifouling agents/products in the UK (1.1).

Assessing geographical patterns in usage (1.2).

Compiling a database relating to information generated through the
project (1.4).

Develop/introduce relevant analytical protocols for the compounds
listed in Section 2. (2.1).
5

To develop/ test models to investigate/predict concentration/effects of
biocides. (2.2)

Conduct coastal surveys at appropriate sites (3.1).

Investigate dissipation/degradation (3.2).

Limited ecotoxicological investigations using flow cytometry will also
be undertaken by PML (4.1).

provide critical comparison
environmental impact (5).
Partner No. 2
Institute for Environmental
Amsterdam, Holland.
Role:
The contribution of the IVM includes:
of
antifouling
Studies
(IVM),
agents
Vrije
regarding
Universiteit,

Surveying of antifouling agents and products being used in the
Netherlands (1.1).

Contributing to the database relating to information generated through
the project (1.4).

Development and/or implementation of suitably sensitive analytical
techniques for compounds listed in Section 2. (2.1).

To survey to assess the extent of contamination of the Dutch coastline
(3.1).

To develop/ test models to investigate/predict concentration/effects of
biocides. (2.2)

Application of functional bioassays to study the endocrine disrupting
effects of antifouling agents including maneb and ziram. (4.2).

Contributions to the integration of the results and the modelling using
different scenario’s for usage (5).
Partner No. 3
Consejo Superior de Investigaciones Cientificas (CSIC), Department
of Environmental Chemistry, Barcelona, Spain.
Role:
The group in Barcelona will carry out the tasks described below:

Surveying antifouling agents/products in Spain (1.1).

Screening of the literature on analytical techniques (1.5).

Solid phase extraction (SPE) techniques followed by LC-MS and
CZE-MS will be used to screen for antifouling pesticides not amenable to
GC/MS analyses. In this way the analysis of ionic compounds is feasible
after enrichment with SPE cartridges (2.1).

Development and evaluation of a new immunoassay for the
determination of Irgarol 1051 to enable to rapid screening of this
ubiquitous antifouling agent in marinas and coastal waters (2.1).

Application of the analytical developments for the monitoring of
antifouling compounds in marinas and coastal waters along Catatonia,
from the Ebro delta area (Tarragona) to the North, with locations like
Barcelona City and Masnou (Barcelona) and Roses (Gerona). Monitoring
will also be conducted in Southern Spain (Almeria). These locations were
known to contain relevant levels of TBT in the past monitoring surveys
(3.1).

Degradation studies using Irgarol 1051 will be carried out in the
laboratory to investigate the formation of possible transformation products
and to estimate the half-life under real environmental conditions (3.2).
6
Partner No. 4
University of Ioannina (UILIC), Laboratory of Industrial Chemistry,
Ioannina, Greece.
Role:
The proposed objectives of this contribution are:

Compile a National survey to include:
- Survey of antifouling agents and products being used in Greece. Details
regarding the registration, importation of antifouling products together with
information on sales and product usage will be collected. Reports detailing
the above information on a national level will be compiled (1.1).
- Identification of the geographical areas potentially at most risk of
contamination in Greece, based on national information concerning
shipping (1.2).

Review on existing analytical methodologies for the compounds
mentioned (1.5) as well as a survey on the available toxicity data on
existing toxicity tests (1.3).

Development and implementation of methods (2.1).
- Development of analytical techniques for the antifouling agents listed in
Section 2. Matrices for analyses will be determined according to the
predicted linear free energy distributions between environmental
compartments. Analytical techniques to be used in quantification will
include high performance liquid chromatography (HPLC), high resolution
capillary gas chromatography (GC) and will involve mass spectrometric
(MS) detection.
- Inter-comparison and inter-calibration of the analytical techniques
developed with the other partner laboratories.

Fieldwork (3.1).
- Assess the extent of contamination in selected Greek coastal areas.
- Investigation of the dissipation of antifouling agents from marinas and
harbours. As part of the surveys undertaken intensive investigation will be
performed at the most contaminated locations to investigate dissipation.

Evaluation of fates of the compounds. The environmental
degradation and transportation will be studied in experimental systems
(3.2).

Development of advisory actions for submission to national and
international authorities and the European Commission (5).
Partner Nos. 5&6 will undertake joint ecotoxicplogical research using shared facilities
to maximise capabilities and outputs.
Partner 5. Göteborg University
Physiology, Göteborg, Sweden.
Partner No. 6.
Institute
Horsholm, Denmark.
Role:
for
(GU),
the
Department
Water
of
Plant
Environment
(VKI),

Short-term toxicity of IRGAROL 1051 and SeaNine 211 to microbial
activity in periphyton and plankton (4.1).

Experimental ecosystem studies of effects on microbial communities
of antifouling agents (Sea-nine 211, Irgarol 1051) (4.3).

Ecosystem studies of effects on microbial communities of antifouling
agents (TBT, Sea-nine 211) around an oil harbour on the Swedish
westcoast and at the Oresund entrance to the Baltic Sea (4.3).
7

Studies of the interaction between effect and fate (how selection of
tolerant organisms will modify the fate of the toxicant) (3.2 & 4)
The Danish partner will be responsible for the Öresund and the plankton
studies and the Swedish partner for the oil harbour and periphyton studies.
However, both partners will participate in each study.
Partner No. 7
National Environmental Research Institute (NERI), Ministry of
Environment and Energy, Roskilde, Denmark.
Role:
NERI will contribute by:

Surveying antifouling agents and products used in Denmark (1.1)

Surveying literature and assessing environmental and toxicological
properties (1.3)

Contributing to the database (1.4)

Undertaking chemical surveys to investigate the extent of
contamination of Danish coastlines for IRGAROL 1051, diuron and
TBT (3.1)

Undertake experiments to investigate fates of IRGAROL 1051 and
TBT (3.2)

Carry out benthic community and microbiological studies to investigate
toxicological impacts from IRGAROL and TBT (4.1 & 4.3)
Partner No. 8
Institut Français de Recherche pour l’Exploitation de la Mer
(IFREMER), Centre de Nantes, Direction de l’Environnement et de
l’Aménagement du Littoral, Département des Polluants Chimiques
(DEL/PC), Nantes, France.
Role:
IFREMER will participate in all five tasks of the project. It contributes
directly to sub-tasks 1.1, 1.2, 1.3, 2.1, 3.1, 4.2 and 5.3:
 Survey of antifouling agents and products being used and marketed in
France (1.1).
 Assessment of geographical patterns / differences in usage (1.2).
 Assessment and selection of antifouling agents on which the studies
will be focused (1.6).
 Development of suitably sensitive analytical techniques (2.1)
 Assessment of the extent of contamination by alternative antifouling
agents of selected Mediterranean and Atlantic coastlines of France (3.1).
 Bioassays to investigate the endocrine disrupting characteristics of
selected antifouling agents (4.2).
 Critical comparison of the products selected regarding environmental
impact (5).
Industrial Partner - Rohm and Haas
Role:
To engage an industrial perspective, one of the major antifouling
manufactures (Rohm and Haas) has agreed to become a partner (costfree) within the project (see Annex 1). Their role will be to advise on their
information compiled on analytical chemistry, environmental chemistry,
microbiology, toxicology and risk assessment.
Invitations to additional industrialists (including paint manufacturers) will be
considered for the debate of findings following integration of results.
8
4. Detailed Description of Tasks
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 (including the responsible scientific officer from the
Commission)
Deliverables:
Minutes of meeting.
Task 1:
Collection and compilation of information
relating to antifouling paint/booster biocide
usage.– month 2
This task has been divided into six sub-tasks as indicated in Table 1.
Sub-task 1.1 – month 2
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
Sub-task 1.2 – month 2
Title
Assessment of geographical patterns/differences in usage.
Responsible:
PML
9
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 subtask 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
Sub-task 1.3 – month 2
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
Sub-task 1.4 – month 5
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.
10
Sub-task 1.5 – month 2
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
Sub-task 1.6 – month 8
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
11
Task 2:
Develop analytical techniques and test models
Sub-task 2.1.- month 3
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, 2,4,5,6tetrachloroisophthalonitrile (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.
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
degradation and ecotoxicology.
Links:
1.4, 1.5, 1.6, 3.1, 3.2, 4, 5
to
investigate
contamination,
Sub-task 2.2 – month 9
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),
12
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
Task 3:
Environmental
experiments
chemical
surveys
and
Sub-task 3.1 - month 7
Title
Assessment of the extent of contamination of European coastlines through
chemical surveys of relevant areas.
Responsible:
PML
Partners:
IVM, CSIC, UILIC, GU, VKI, NERI, IFREMER
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.
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
Sub-task 3.2 – month 17
Title
Laboratory studies to assess the degree of physical and chemical
degradation of the antifouling agents..
Responsible:
UILIC
Partners:
CSIC, PML
Duration:
13 months
Objectives:
Laboratory studies to assess the degree of physical and chemical
degradation of the antifouling agents
13
Methods:
In the literature, few data are available regarding the persistence of
antifouling agents, some of which are conflicting. In this project, a
consistent set of degradation studies will be carried out so as to obtain
reliable, comparable information for compounds of interest.
Deliverables:
Information concerning degradation/dissipation
biocides (to be summarised in major report 5).
Links:
1.4, 1.5, 1.6, 2.1, 2.2, 3.1, 4, 5
Task 4:
Ecotoxicological Investigations
of
selected
booster
Sub-task 4.1 – month 3
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, Sea-nine 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
Sub-task 4.2 – month 17
Title
Bioassays to investigate the endocrine disrupting characteristics of the
antifouling agents.
Responsible:
IVM
Partners:
IFREMER
Duration:
10 months
Objectives:
To investigate the endocrine disrupting characteristics of the antifouling
agents (including IRGAROL 1051, Maneb and Ziram) using bioassays.
Methods:
In this sub-task, the antifouling agents will be tested with bioassays which
indicate estrogenic activity, e.g. the yeast screen assay and an estrogenic
assay based on a mammalian breast cancer celline.
Deliverables:
Information to judge the endocrine disrupting potential of the booster
biocides (to be summarised in major report 7).
Links:
1.3, 1.4, 1.6, 2.2, 3.1, 3.2, 4.3, 5
14
Sub-task 4.3 – month 26
Title
Investigate whether effects observed under laboratory conditions occur
under (semi-) field conditions.
Responsible:
GU
Partners:
VKI, NERI, IFREMER
Duration:
8 months
Objectives:
To investigate the effects observed in laboratory under (semi-) field
conditions.
Methods:
The bioassays tested in the above sub-tasks will predict effects. The
validity of these predictions will be checked with a limited number of tests
under semi-field conditions.
Deliverables:
An assessment of environmental damage through booster biocide usage
(major report 8).
Links:
1.3, 1.4, 1.6, 2.2, 3, 4.1, 4.2, 5
Task 5:
Integrate results and evaluate risks
Sub-task 5.1 – month 34
Title
Update/extend the database (see section 5.2).
Responsible:
PML
Partners:
IVM, CSIC, UILIC, GU, VKI, NERI, IFREMER
Duration:
2 months
Objectives:
Additional data generated in this project will be added to the database
developed in sub-task 1.4.
Deliverables:
Updated database.
Links:
1.4, 1.6, 3.1, 3.2, 4.1, 4.2, 4.3
Sub-task 5.2 – month 21
Title
Use the database and models to predict concentration levels and effects in
selected European coastal zones using different scenario’s for usage.
Responsible:
IVM
Partners:
PML, CSIC, UILIC, GU, VKI, NERI, IFREMER
Duration:
19 months
Objectives:
To use the database (sub-task 5.1) (see section 5.2) and models to predict
concentration levels (sub-task 2.2) and effects (sub-task 4.3) in selected
European coastal zones using different scenario’s for usage will be
integrated to assess environmental distributions and potential effects.
Deliverables:
Models and contribution to final report.
Links:
2.2, 4.3, 5.1
15
Sub-task 5.3 – month 40
Title
Undertake a critical comparison of the products selected regarding
environmental impact.
Responsible:
PML
Partners:
IVM, CSIC, UILIC, GU, VKI, NERI, IFREMER
Duration:
2 months
Objectives:
To critically compare the potential environmental impact of the products
selected.
Deliverables:
Assessment concerning booster biocide usage providing guidance to
environmental managers (summary in the Final Report).
Links:
5.1, 5.2
5. Management of the Project
5.1 Organisation
The project is coordinated by PML. A diagram showing the organisational structure for the key
activities is given in Figure 1 and a management plan and timetable are given in Table 1. PML
is responsible for ensuring that the semi-annual and annual reports are completed, for
coordinating the steering committee and for general communication with disciplinary leaders.
Primary communication will be by e-mail. The project will be managed by a Steering
Committee comprising PML, IVM, CSIC, UILIC, GU, VKI, NERI, IFREMER. The Steering
Committee has responsibilities for ensuring that all tasks and sub-tasks are carried out.
Responsibility for the individual/specific sub-tasks are designated to those considered to be
well suited. The sub-tasks will be led by the sub-task co-ordinator viz:
Sub-task 1.1 PML
Sub-task 1.2 PML
Sub-task 1.3 GU
Sub-task 1.4 PML
Sub-task 1.5 CSIC
Sub-task 1.6 PML
Sub-task 2.1 CSIC
Sub-task 2.2 IVM
Sub-task 3.1 PML
Sub-task 3.2 UILIC
Sub-task 4.1 GU
Sub-task 4.2 IVM
Sub-task 4.3 GU
Sub-task 5.1 PML
Sub-task 5.2 IVM
Sub-task 5.3 PML
To engage an industrial perspective, one of the major antifouling manufactures has agreed to
become a partner (cost-free) within the project (see Annex 1). Invitations to additional
industrialists (including paint manufacturers) will be considered for the debate of findings
following integration of results.
16
Collection of
data on
antifouling
usage (PML)
All Partners
PML
IVM
Method
Development
Project
Analytical
Chemistry
(CSIC)
Modelling
(IVM)
Degradation
Studies
(UILIC)
(PML)
IFREMER
PML
Coastal
Surveys
(PML)
Environmental
Chemistry
Coordinator
UILIC
All Partners
CSIC
PML
VKI
Ecotoxicology
Toxic Effects
(GU)
NERI
PML
Endocrine
Disruption
(IVM)
Data Base
(PML)
All Partners
IFREMER
Modelling
(IVM)
All Partners
Critical
Comparison
of Products
(PML)
All Partners
Figure 1. The Organisational Structure for the Key Activities.
17
5.2 Data Management
Information and Data Flow
Within the project it will be essential that all partners have access to both information and
data.
The ACE Project Co-ordinator (PML) will be responsible for the project data management. An
ACE Data Advisory team1 will be formed at the start of the project. It will include
representatives from all participating organisations and be chaired by the ACE Project Coordinator. Data, documentation and metadata will be collated and indexed in a database
produced and managed by PML (sub task 1.4). An ACE web site will be produced at the start
of the project to act as the focus for information dissemination. This web site (also based at
PML) and the database will be available to all ACE partners across the Internet (with
appropriate security).
A series of scientific papers will be published in peer-reviewed international journals such as
Marine Pollution Bulletin and Science of the Total Environment, Environmental Science and
Technology, Trends in Analytical Chemistry etc. Practical applications of the work will also be
disseminated in popular publications such as New Scientist, which are more widely read by
managers. Brochures will also be prepared and distributed to interested parties which will
incorporate user groups including managers and politicians who will be specifically targeted.
Data Documentation
All datasets will have an associated EDMED 2 form documenting them. The fields on this form
will be extended to include the following:
Sample collection: Equipment used, measuring platform, method of deployment, calibration,
sampling frequency, sampling, environmental conditions, limitation of sampling strategy.
Sample processing: sample preservation method, where processed, processing steps
(instruments, methods, etc), error corrections made, precision, accuracy, limits of detection,
limitations of processing.
Data processing: steps in processing, methods of data reduction, statistical methods,
software used, and limitations.
Quality assurance performed: description of steps taken to provide quality assurance.
Note: Where possible this documentation will use references rather than duplicate
information.
Data Quality
The use of the extended EDMED form (as described in section 2 above) should ensure that
all the information relating to the data quality is captured. The data advisory team will review a
subset of the extended EDMED forms to ensure all necessary quality information is being
captured.
Data quality will be on the agenda for all meetings of the ACE data advisory team.
Technical Issues
The ACE database will be developed in Microsoft Access and incorporate a user-friendly
interface. The relational database will be designed with referential integrity to ensure
consistency of the data. This will be done through the use of validation rules, cascading
deletes etc. A scheme for the data relationships is shown in figure 1. The database will be
structured to allow for its integration into spatial software handling systems such as
1
See the MAST document "A guideline for Project Data Management" for further details of
the teams composition and role.
2
EDMED = European Directory of Marine Environmental Data, a MAST funded project coordinated by the British Oceanographic data centre (BODC).
18
Geographical Information Systems. Where possible documents will be produced in Adobe
Acrobat portable document format (pdf) to ensure good availability.
Dissemination
The final database and web site will be published on a CD-ROM six months after completion
of the project. This work will be managed by PML. The EDMED forms will also be sent to
BODC for inclusion in the European Directory of Marine Environmental Data.
Longevity and Final Archiving
The published CD-ROM will be archived at PML for 10 years. Copies of the CDROM will also
be sent to the British Oceanographic Data Centre. ASCII versions of all data will also be
included in order to overcome software reader redundancy
5.3 Data Quality
Analyses: Analytical quality assurance will include use of high quality authentic standards,
the use of internal standards, the adoption of “good laboratory practice” procedures and, in
the absence of certified reference materials, intercomparison exercises between the
participating laboratories will be organised.
Quality control of the modelling work: For validation of the model the results will need to
be compared with existing literature data from laboratory studies and field observations. The
necessary information can partially be found in the scientific literature. For some compounds
very little data exist, but good contacts with the manufacturers are expected to improve our
access to internal reports and other "grey literature" As the project continues more data will
become available for validation.
5.4 Meetings and Workshops
Following commencement of the project, PML will convene a workshop in Plymouth with all
participating laboratories in order to develop fully the details of the programme. Points of
attention are:
 Specification of short and medium term objectives with corresponding deadlines, agreed
by all.
 A communication programme between participants and co-workers, including an interim
report (mid-yearly period) and annual report (end of yearly period).
 With specific intervals, each participant will provide PML with a progress report. A model
for this report will be prepared. The Project Co-ordinator will assemble these reports and
distribute it to all.
 All communication between participants will be copied to the Project Co-ordinator.
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 (see Table 1) and venues will be agreed at the
inception workshop. 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.
5.5 Milestones
1. Construction of database of information relating to antifouling paint/booster biocide usage
and choice of compounds on which studies will be focused (major report 1). Month 10.
2. Production of tested/proven analytical protocols to quantify the selected “booster
biocides” (major report 2.). Month 12.
19
3. Selection and testing of models to predict concentrations and effects (major report 3).
Month 29.
4. Assessment of the extent of contamination of coastlines in participating countries (major
report 4). Month 29.
5. Completion of investigations into transport and degradation studies of the biocides (major
report 5). Month 29.
6. Production of relevant bioassays to investigate toxicity (major report 6). Month 20.
7. Completion of investigations into endocrine disrupting characteristics of the antifouling
agents (major report 7). Month 26.
8. Completion of investigations into ecotoxicological effects under semi-field conditions
(major report 8). Month 33.
5.6 Reports
Management reports: will be issued 6 monthly and are the responsibility of the Project Coordinator.
Annual scientific and technical progress reports: will be issued after, and include reports
of, the annual workshops: responsibility Project Co-ordinator.
Major scientific reports will be issued following completion of the sub-tasks to which they
are linked (see Milestones above). Major reports are the responsibility of the Partner
responsible for the sub-task to which they pertain.
The final report will be the responsibility of the Project Co-ordinator and will include:

A consolidated management and progress report,

A final scientific and technical report,

A report on exploitation,

Lists of published and planned scientific papers with appropriate means of dissemination
of abstracts.
Responsibility Project Co-ordinator.
6. Dissemination of Results
A series of scientific papers will be published in peer-reviewed international journals such as
Marine Pollution Bulletin and Science of the Total Environment, Environmental Science and
Technology, Trends in Analytical Chemistry etc. Practical applications of the work will also be
disseminated in popular publications such as New Scientist, which are more widely read by
managers. An Internet ACE web site will be generated to afford widespread access to
information and data. Brochures will also be prepared and distributed to interested parties
which will incorporate user groups including managers and politicians who will be specifically
targeted.
The final database and web site will be published on a CD-ROM six months after completion
of the project. This work will be managed by PML. The EDMED forms will also be sent to
BODC for inclusion in the European Directory of Marine Environmental Data.
20
7. Work Planning Schedule.
Please see table 1.
21
Task
Sub-Task Description
Month
Partner
UK NL ES GR SE DK DK FR
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43
Inception workshop
1
Collection and compilation of information relating to
antifouling paint/booster biocide usage
1.1
Surveys of antifouling agents and products being
manufactured
1.2
Assessment of geographical patterns / differences in usage;
1.3
1.4
1.5
1.6
2
2.1
2.2
3
3.1
3.2
4
4.1
4.2
4.3
5
5.1
5.2
5.3
Survey and critical assessment of the environmental and
toxicological properties.
The development of a concise database with the information
obtained;
Screening of literature on analytical techniques used for the
different antifouling agents;
Information available will be assessed and antifouling
agents on which the studies will be focused will be selected
Develop analytical techniques and test models
The development, testing and intercomparison of suitably
sensitive analytical techniques
Implementation of models capable to predict concentrations
and effects for different scenario’s
Environmental chemical surveys and experiments
Assessment of the extent of contamination of European
coastlines through chemical surveys of relevant areas
Laboratory studies to assess the degree of physical and
chemical degradation of the antifouling agents.
Ecotoxicological Investigations
Bioassays to investigate toxic effects of the selected
antifouling agents
Bioassays to investigate the endocrine disrupting
characteristics of the antifouling agents;
Investigate whether effects observed under laboratory
conditions occur under (semi-) field conditions
Integrate results and evaluate risks
Update/extend the database
1
2
3
4
5
6
7
8
R
P
P
P
P
P
P
P
R
P
P
P
P
P
P
P
R
P
P
P
P
P
P
P
R
P
P
P
P
P
P
P
P
P
P
P
R
MR1
P
P
P
R
P
R
P
P
P
P
P
R
P
MR3
P
R
MR4
R
P
P
P
MR5
P
P
R
MR2
MR6
P
MR7
Table 1: Workplan (Seasonal requirements for some studies may necessitate timing adjustments relative to the project start date)
P
P
P
R
P
P
R
FR
P
P
MR8
Use the database and models to predict concentration
levels and effects in selected European coastal zones using
different scenario’s for usage
Undertake a critical comparison of the products selected
regarding environmental impact
Workshops
Progress Reports
Notes: R - Responsibility; P - Partner; Grey squares indicate milestones; MR1 to MR8 indicate production of major reports; FR - Final report;
P
R
P
P
P
R
P
P
P
P
P
P
P
P
R
P
P
P
P
P
P
R
P
P
P
P
P
P
P