Review articleWorldwide occurrence and effects of antifouling paint booster biocides in the aquatic environment: a review
Introduction
The need for effective antifoulants, which prevent the settlement and growth of marine organisms on submerged structures, such as oil rig supports, buoys, fish cages and ship's hulls, is recognised universally Evans et al., 2000, Boxall et al., 2000. For many years, tributyltin (TBT) compounds were the most widely used active ingredients in paint formulations but it has been regulated internationally since 1990 due to its severe impact on the aquatic ecosystem (Fent, 1996). Legislation in many countries banned the application of TBT-based paints to small vessels (<25 m) (European Community, 1989) and the International Maritime Organization (IMO), Marine Environment Protection Committee (MEPC), have recently announced a proposed ban on the use of TBT as an antifouling agent on ships. This ban is likely to be introduced in 2003 and will lead to an increase in vessels using alternative “TBT-free” coatings containing copper combined with organic booster biocides IMO, 1998, Christen, 1999, Julian, 1999. Biocide containing coatings are already used and applied to the hulls of ships and boats to prevent the growth of bacteria, macroalgae, mussels and other invertebrates. Worldwide around 18 compounds are currently used as antifouling biocides Yonehara, 2000, Thomas, 2001. Nine of them (chlorothalonil, dichlofluanid, diuron, Irgarol 1051, sea-nine 211, TCMS pyridine, TCMTB, zinc pyrithione and zineb) are approved for use by Health and Safety Executive (HSE) in amateur and professional antifouling products marketed in the UK HMSO, 1998, Voulvoulis et al., 2002a. These biocides are also the most frequently used in many countries. As a result, important coastal concentrations have been found in areas of high yachting activity, particularly in marinas and sportive harbors. Voulvoulis et al. (1999a) reviewed 11 alternative antifouling biocides and concluded that there was not enough information on such chemicals to perform a sound environmental risk assessment. Since these alternatives to TBT are also toxic, their contamination in the aquatic environment has been a topic of increasing importance the last years.
An initial assessment of antifouling paint biocide inputs associated with high-pressure hosing activities suggests that in terms of total biocide release, the main source of biocide is release from painted hulls during the lifetime of the paint. However, the majority of biocide released during hosing activities is in the form of paint particles that can become incorporated in sediments (Thomas et al., 2002). Dissipation from the hulls of vessels relate to leaching rates, the number (and treatment) of vessels, water movements, degradation rates and sorptive behaviour. Studies have shown that two of the most popular biocides in use, Irgarol 1051 and diuron, persist in surface waters, whilst other biocides, such as Sea-nine 211, dichlofluanid, zinc pyrithione and chlorothalonil, disappear quickly Thomas, 2001, Thomas et al., 2002, Thomas et al., 2003. Although the physicochemical properties of the compounds differ significantly and some are rapidly degraded, these compounds will also accumulate in marine sediments if introduced as paint particles.
A review by the UK Health and Safety Executive (HSE) as part of the European Commission's Biocidal Products derivative (98/8/EC) has led to restrictions in the use of booster biocides (Thomas et al., 2002). The results of these restrictions in the UK is that only paints containing dichlofluanid, zinc pyrithione or zineb as the active biocide can be applied on vessels <25 m in length. In addition to these three biocides, Irgarol 1051, chlorothalonil and Sea-nine 211 containing formulations can also be used on vessels >25 m in length. Diuron is no longer approved for use as an active ingredient in antifouling paints, on any size of vessel. Other European countries as Denmark and Sweden have also restricted the use of paints containing Irgarol 1051 and Diuron to boats >25 m in length. A comparative general environmental assessment of biocides used in antifouling paints was recently reported by Voulvoulis et al. (2002a), provided support for the use of the precautionary principle with respect to policies on antifouling products. There is therefore a requirement for information on the usage and concentrations of biocides that would provide the necessary data for modeling processes. There is also need for monitoring data that can be used in risk assessment process and which can be used to validate existing models. The data could also assist in the prioritization of monitoring studies and the development of analytical techniques.
This review will focus on the available data concerning the occurrence of the most used biocides in the aquatic environment worldwide. Some of the previous available data dealing with the environmental behavior of antifouling paint booster biocides are also reported in order to discuss the detected levels of contamination. The fate and effects of the biocides were studied by other authors Thomas, 2001, Thomas et al., 2002, Thomas et al., 2003, Ranke and Jarstoff, 2000, Jacobson and Willingham, 2000, Hall et al., 1999, Caux et al., 1996, Madsen et al., 2000 and consequently only very recently reported studies are reviewed.
Section snippets
Irgarol 1051
The s-triazine herbicide Irgarol 1051 was the first booster biocide to gain prominence as an environmental contaminant. The presence of Irgarol was reported in 1993 in the surface waters of marinas on the Côte d' Azur, France, by Readman et al. (1993) at concentrations up to 1700 ng/l. Since 1993, the occurrence of Irgarol 1051 has been reported in a number of other European countries as well as in USA, Japan, Australia and Bermuda (Table 1). In the UK, Irgarol 1051 has been found in surveys
Conclusions
The present study reviews the available data on the worldwide occurrence of antifouling paint booster biocides in the aquatic environment. Important coastal concentrations were detected in areas of high yachting activity, particularly in marinas and harbours as a consequence of their increased use in antifouling paints. Continuous monitoring of biocides concentration profiles in water, sediment and biota is needed to support information that should lead to concerted action to ban or regulate
References (103)
- et al.
Multiresidue method for the analysis of five antifouling agents in marine and coastal waters by gas-chromatography-mass spectrometry with large-volume injection
J. Chromatogr. A
(2000) - et al.
Transportation of pesticides in Estuaries of the Axios, Loudias and Aliakmon rivers (Thermaikos Gulf), Greece
Sci. Total Environ.
(1994) - et al.
Antifouling paint booster biocide contamination in Greek marine sediments
Chemosphere
(2002) - et al.
Organotin and Irgarol 1051 contamination in Singapore coastal waters
Mar. Pollut. Bull.
(2002) - et al.
Concentrations of the antifouling compound Irgarol 1051 and of organotins in water and sediments of German North and Baltic Sea marinas
Mar. Pollut. Bull.
(2000) - et al.
Seasonal variability in the concentrations of Irgarol 1051 in Brighton marina, UK; including the impact of dredging
Mar. Pollut. Bull.
(2003) - et al.
Inputs, monitoring and fate modelling of antifouling biocides in UK Estuaries
Mar. Pollut. Bull.
(2000) - et al.
Partitioning of marine antifoulants in the marine environment
Sci. Total Environ.
(2002) - et al.
Contamination of the coastal waters of Bermuda by organotins and the triazine herbicide Irgarol 1051
Mar. Pollut. Bull.
(2001) - et al.
Toxic effects of the antifouling agent Irgarol 1051 on periphyton communities in coastal water microcosms
Mar. Pollut. Bull.
(1996)
The toxicology and metabolism of chlorothalonil in fish: I. Lethal levels for Salmo gairdneri, Galaxias maculatus, G. truttaccus and G. auratus and the fate of C-14-TCIN in S. gairdneri
Aquat. Toxicol.
Monitoring of priority pesticides and other organic pollutants in river water from Portugal by gas-chromatography-mass spectrometry and liquid chromatography-atmospheric pressure chemical ionization mass spectrometry
J. Chromatogr. A
The TBT ban: out of the frying pan into the fire?
Mar. Pollut. Bull.
Toxicity evaluation of single and mixed antifouling biocides measured with acute toxicity bioassays
Anal. Chim. Acta
Simultaneous determination of antifouling herbicides in marina water samples by on-line solid-phase extraction followed by liquid chromatography-mass spectroscopy
J. Chromatogr. A
Identification of a new degradation product of the antifouling agent Irgarol 1051 in natural samples
J. Chromatogr. A
Magnitude and distribution of antropegenic contaminants in salt-marsh sediments of the Essex coast UK: 2. Selected metals and metalloids
Sci. Total Environ.
Separation of phenylurea pesticides by ion-interaction reversed-phase high performance liquid chromatography: diuron determination in lagoon water
J. Chromatogr. A
A survey of Southern England coastal waters for the s-Triazine antifouling compound Irgarol 1051
Mar. Pollut. Bull.
Micro-organic compounds in the Humber rivers
Sci. Total Environ.
Sea-nine antifoulant: an environmentally acceptable alternative to organotin antifoulants
Sci. Total Environ.
Effects of new antifouling compounds on the development of sea urchin
Mar. Pollut. Bull.
Determination of diuron and the antifouling paint biocide Irgarol 1051 in Dutch marinas and coastal waters
J. Chromatogr. A
Long term effect of Sea-Nine on natural coastal phytoplankton communities assessed by pollution induced community tolerance
Aquat. Toxicol.
Transformation of the new antifouling compound Irgarol 1051 by Phanerochaete chrysosporium
Water Res.
Mercuric chloride-catalyzed hydrolysis of the new antifouling compound Irgarol 1051
Water Res.
Survey for the occurrence of the new antifouling compound Irgarol 1051 in the aquatic environment
Water Res.
Short term response and recovery of Zostera capricorni photosynthesis after herbicide exposure
Aquat. Bot.
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
J. Chromatogr. A
Toxic effects of Irgarol 1051 on phytoplankton and macrophytes in Lake Geneva
Water Res.
Photodegradation of the antifouling compounds Irgarol 1051 and diuron released from a commercial antifouling paint
Chemosphere
Fate and ecotoxicity of the new antifouling compound Irgarol 1051 in the aquatic environment
Water Res.
Phytotoxicity of the new antifouling compound Irgarol 1051 and a major degradation product
Mar. Pollut. Bull.
Toxicity evaluation of new antifouling compounds using suspension-cultured fish cells
Chemosphere
Antifouling herbicides in the coastal waters of western Japan
Mar. Pollut. Bull.
Inhibition of coral photosynthesis by the antifouling herbicide Irgarol 1051
Mar. Pollut. Bull.
Photodegradation and stability of chlorothalonil in water studied by solid phase disk extraction, followed by gas chromatographic techniques
J. Chromatogr. A
Trace determination of antifouling compounds by on-line solid phase extraction-gas chromatography-mass spectrometry
J. Chromatogr. A.
Photodegradation study of the antifouling booster biocide dichlofluanid in aqueous media by gas chromatographic techniques
J. Chromatogr. A
Aquatic phototransformation study of the antifouling agent Sea-nine 211: identification of by-products and the reaction pathway by gas-chromatography-mass spectrometry
J. Chromatogr. A
Study of chlorothalonil photodegradation in natural waters and in the presence of humic substances
Chemosphere
Levels of antifoulant irgarol 1051 in the Conwy Marina, North Wales
Chemosphere
Occurrence of the marine antifouling agent irgarol 1051 within the plymouth sound locality: implications for the Green Macroalga Enteromorpha intestinalis
Mar. Pollut. Bull.
Risk posed by the antifouling agent Irgarol 1051 to the seagrass, Zostera marina
Aquat. Toxicol.
Occurrence of the antifouling herbicide Irgarol 1051, within coastal-water seagrasses from Queensland, Australia
Mar. Pollut. Bull.
Ultra-trace-level determination of the antifouling agent Irgarol 1051 by gas chromatography with tandem mass spectrometric detection
J. Chromatogr. A
Gross fluxes an estuarine behaviour of pesticides in the Scheldt Estuary (1995–1997)
Environ. Pollut.
Determination of selected antifouling booster biocides by high-performance liquid-chromatography-atmospheric pressure chemical ionisation mass spectrometry
J. Chromatogr. A
Determination of the antifouling agent zinc pyrithione in water samples by copper chelate formation and high-performance liquid chromatography-atmospheric pressure chemical ionisation mass spectrometry
J. Chromatogr. A
Antifouling paint booster biocide contamination in UK Marine sediments
Mar. Pollut. Bull.
Cited by (538)
Hull-cleaning wastewater poses serious acute and chronic toxicity to a marine mysid—A multigenerational study
2024, Journal of Hazardous MaterialsIndirect photodegradation of zinc pyrithione: The effect of chromophoric dissolved organic matter components and seawater factors
2024, Journal of Environmental Chemical EngineeringSulfated phenolic polymers as non-toxic antifouling agents
2024, European Polymer JournalChemical contaminants in blood and their implications in chronic diseases
2024, Journal of Hazardous MaterialsDevelopmental cardiotoxicity of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT) in marine medaka (Oryzias melastigma)
2024, Journal of Hazardous Materials