FLUORIDE ACTION NETWORK PESTICIDE PROJECT
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Dichlofluanid. Assessment of antifouling agents in coastal environments.
ASSESSMENT OF ANTIFOULING AGENTS IN COASTAL ENVIRONMENTS (ACE)
MAS3-CT98-0178
Management Report (February 2000 -July 2000)
James W Readman (Plymouth Marine Laboratory, UK)
Executive Summary
During the reporting period, the focus of ACE moved away from collection and compilation of information to the generation of research results. The extent of contamination of European coastlines is being assessed (sub-task 3.1) and testing of environmental models has commenced (sub-task 2.2). Substantial mesocosm and field experiments have been undertaken to investigate biological effects (sub-task 4.1). Research into degradation of the compounds (sub-task 3.2) and bioassays to investigate any endocrine disruption characteristics have recently commenced (sub-task 4.2). Several publications resulting from the research (and acknowledging support through ACE) have already appeared in International journals and others are in press.
Task 2 Develop analytical techniques and test models.
Sub-tasks:
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-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.
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.
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
Partners continue to be prolific in the development of analytical techniques. The following papers have been compiled:
Barceló, D. (1999) Sample handling and analysis of pesticides and their transformation products in water matrices by liquid chromatographic techniques. Elsevier Science BV, pp 155-207.
Castillo, M and Barceló, D. (1999) Identification of polar toxicants in industrial wastewaters using toxicity-based fractionation with liquid chromatography/mass spectrometry. Analytical Chemistry, Vol. 71, Number 17 pp 3769-3776
Ferrer, I and Barceló, D. (1999) 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 pp 197-206
Ferrer, I, Thurman, EM and Barceló, D. (2000) First LC/MS Determination of Cyanazine amide, Cyanazine Acid, and Cyanazine in Groundwater Samples. Environmental Science and Technology, Vol 34, No 4, pp 714-718.
Lampropoulou DA, Konstantinou, IK and Albanis, TA. Determination of fungicides and antifouling compounds in natural waters using SPME techniques and gas chromatography coupled with electron capture and mass spectrometric detection, 5th International Conference on Environmental Pollution, Thessaloniki 28-30 August 2000
Lampropoulou, DA, Konstantinou, IK and Albanis, TA (2000), Determination of antifouling compounds in natural waters using solid phase microextraction (SPME) and gas chromatography coupled with electron capture and mass spectrometric detection, submitted to J. Chromatography
Martinez, K, Ferrer, I and Barceló, D. 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.
Martnez, K, Ferrer, I and Barceló, D. (2000) Part-per-trillion level determination of antifouling pesticides and their byproducts in seawater samples by off-line solid-phase extraction followed by high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry. Journal of Chromatography A, Vol. 879, pp 27-37.
Peñuela GA and Barceló, D. (2000) Comparative Photodegradation study of atrazine and deethylatrazine in water samples containing titanium dioxide/hydrogen peroxide and ferric chloride/hydrogen peroxide. Journal of A.O.A.C. Intl., 83 pp 53-60
Peñuela GA, Ferrer, I and Barceló, D. (2000) Identification of new photodegradation byproducts of the antifouling agent Irgarol in seawater samples. Intern.J. Environ. Anal. Chem (in press)
Most recently CSIC have been working on the identification of a degradation products of the antifouling agent Irgarol 1051 in natural samples. A major degradation product was detected at trace levels in seawater and sediment samples collected from several marinas on the Mediterranean coast. This degradation product was identified as 2-methylthio-4-tert-butylamino-s-triazine. The unequivocal identification of this compound in seawater samples was carried out by solid-phase extraction (SPE) coupled on-line with liquid chromatography/atmospheric pressure chemical ionization/mass spectrometry (LC/APCI/MS).
Analytical techniques developed by IVM, UILIC, PML and IFREMER also continue to be applied in sub-task 3.1.
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 scenarios 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 is being led by the Dutch partners and is on-track. A computer model to generate predicted environmental concentrations for antifouling products in the marine environment has been developed and was recently presented at the Third SETAC World Congress. The following articles have been compiled:
van Hattum, B, Baart, A, Boon, J , Steen, RJCA and Ariese, F. (2000). Development of a computer model (MAM-PEC) to predict marine environmental concentrations of antifouling agents. Poster presentation at Third SETAC World Congress, 21-25 May 2000, Brighton, UK.
Van Hattum, B, Baart, AC, Boon, JG, Steen, RJCA and Ariese, F. (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.
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.
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
Work has continued by all partners to assess the extent of contamination of European coastal waters by booster biocides.
In the UK, sampling primarily focussed on areas of yachting activity on the south coast and season variability has been assessed. In addition, dissipation of Irgarol from the Humber Estuary is being assessed through analyses of samples taken during a cruise on the RRS Challenger (16-27 September 1999).
The Dutch partners have been working on the Scheldt Estuary.
Extensive surveys in Spain have been carried out for diuron, Irgarol 1051, SeaNine 211, chlorothalonil, dichlofluanid, (2-thiocyanomethylthio) benzothiazole (TCMTB), and three degradation products (demethyldiuron, 3,4-dichlorophenylurea and 2-methylthio-4-tert-butylamino-s-triazine). Enclosed harbours from Catalonia and Almería (Spanish Mediterranean coast) have been investigated. Nine points were sampled along the Catalan coast: Barcelona Olympic port, Masnou, Blanes, Sant Carles de la Ràpita, Tarragona, Cambrils and Salou marinas as well as the Cambrils and Tarragona fishing harbours and in marinas and ports from Almeria: Aguadulce port, Almería port, Almerimar fishing harbour and Almerimar marina. The main pollutants found were diuron and Irgarol 1051 at concentrations of up to 2.19 µg/l and 0.33 µg/l, respectively. SeaNine 211 was also found at up to 3.7 µg/l during the summer of 1999. Low concentrations of dichlofluanid and the above mentioned degradation products were detected for the first time in samples from the Spanish coasts. Chlorothalonil and TCMTB were not found at concentrations higher than 1 and 20 ng/l respectively which were the limits of determination (LOD) of the method. In general, the contamination at the different marinas is higher at the end of spring and in summer when the boating activities are highest. This data is being compiled for publication.
In Greece, water and sediment samples from various marinas and ports have already been analysed for chlorothalonil, dichlofluanid, Irgarol and diuron. The sampling stations have included Eleusina marina, Pirgeus Port, Halkida Marina, Kalamaria Port, Patras and Volos port.
Samples from the Swedish coastline have been taken and stored awaiting analyses of Irgarol and SeaNine, as have samples from three marinas around Sjaelland and on the Danish coast (during July 2000). In Denmark, a major study is planned for next year.
Finally, IFREMER have introduced and tested the relevant analytical techniques and surveys are underway.
To date, the following publications have been compiled:
Steen, R, van der Vaart, J, Hiep, M, van Hattum, B, Cofino, W and Brinkman, U. Gross Fluxes and estuarine behaviour of pesticides in the Scheldt Estuary (1995-1997). Submitted to: Environmental Chemistry and Toxicology.
Steen, RJCA, Jacobsen, J, Ariese, F, and van Hattum, B. (2000). Monitoring Sea-Nine 211 Antifouling Agent in a Danish Harbor. Poster presentation at Third SETAC World Congress, 21-25 May 2000, Brighton, UK
Steen, RJCA, Jacobson, J, Ariese, F and van Hattum, B. (1999). Monitoring Sea-nine 211 Antifouling agent in a Danish Harbor. IVM-E99/10, Institute for Environmental Studies, Amsterdam.
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
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 of selected booster biocides (to be summarised in major report 5).
Links: 1.4, 1.5, 1.6, 2.1, 2.2, 3.1, 4, 5
Research into degradation of antifouling agents is underway and is ahead of schedule. Indeed, the following publications already describe results:
Larsen, D, Wagner, I and Gustavson, K. Degradation of Sea-Nine in coastal water. (submitted)
Sakkas, V, Konstantinou, IK and Albanis, T A. Photocatalytic degradation of antifouling compounds. 1st European Conference on pesticides and relative organic micropollutants in environment, Ioannina 5-8 October 2000.
Sakkas, V, Konstantinou, IK and Albanis, TA. Photodegradation of antifouling biocides in water under simulated sunlight, 5th International Conference on Environmental Pollution, Thessaloniki 28-30 August 2000.
Task 4 Conduct ecotoxicological investigations.
Sub-tasks:
- 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
Three major studies have been completed by the Swedish scientists during summer 2000, although data are not yet fully analysed.
Field study of Irgarol effects was made in the Fiskebäckskil area on the Swedish west coast. The PICT methodology was used to detect effects of Irgarol and to relate them to analysed concentrations (Barcelona group) in a spatial and temporal gradient from a small marina (300 boats) to the outer archipelago. A late tolerance increase was observed, which in our preliminary interpretation suggests that Irgraol is exerting selection pressure on the algal community but that it takes a long and consistent exposure for the tolerance to become detectable. This is similar to the responses to other triazine herbicides.
A plankton mesocosm experiment was made in August 2000 at Kristineberg Marine Research Station. Both Irgarol 1051 and SeaNine 211 were assessed in parallel experiments. Focus was on the phytoplankton and the effects indicators were species composition, photosynthestic activity (based on PAM measurements) and induced community tolerance (quantified as increases in the tolerance of photosynthesis). In collaboration with Danish and German scientists, effects on nutrient content, bacteria and zooplankton were also measured. Samples for chemical analyses of Irgarol and SeaNine were taken (Barcelona group).
A mixture toxicity experiment with TBT, Irgarol and SeaNine was made in collaboration with another EU project (PREDICT). To our knowledge this is the first long-term community test involving three component mixtures. The analytical chemistry will be undertaken by ACE scientists (Barcelona and Copenhagen groups) and the mixture toxicity evaluated by PREDICT scientists.
The analytical work of all these experiments is under way but will not be completed until late autumn 2000 when we expect preliminary results to be available.
NERI also took part in the joint mesocosm experiment described above. The following parameters were investigated by NERI:
pigment composition, as a measure for changes in phytoplankton population
heterotrophic nanoflagellate composition
bacterial production
bacterial community composition
bacterial motility (in co-operation with Dr Hans-Peter Grossart, Oldenburg University)
SeaNine and Irgarol concentrations
egg production and hatching rate for Acartia sp. as a measure of toxicity and secondary effects
In addition, NERI also contributed to the PICT-experiments for phytoplankton through size-fractionation of the phytoplankton community to complement the total community PICT undertaken by the Göteborg group. Dr Grossart also performed PICT on bacteria motility for SeaNine.
Publications (with acknowledgements to this EU Project)
Readman. JW et al. Flow cytometry and pigment analyses reveal the susceptibility of prymnesiophytes to a triazine.
Wagner I, Larsen D and Gustavson, K. Effects of Sea-Nine on marine phytoplankton communities. (submitted)
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
This work has recently commenced and is now underway.
Initiatives for the dissemination of results
The ACE web site (www.pml.ac.uk/ace) is being updated with the information generated (and described in the first Annual Report).
All publications fully acknowledge support through the European Commission.
In addition, two general presentations of the programme have been made by the Co-ordinator:
Readman, JW. (2000) Recent developments in antifouling booster biocide research. To be published in proceedings of the 1st European Conference on Pesticides and Related Organic Micropollutants in the Environment. (Ioannina, Greece. 5 8 October 2000).
Readman, JW. (2000) Poster presentation with an Extended Abstract in the proceedings from the EurOCEAN Conference. (Hamburg, Germany. 29 August 2 September 2000)