Elsevier

Environment International

Volume 30, Issue 2, April 2004, Pages 235-248
Environment International

Review article
Worldwide occurrence and effects of antifouling paint booster biocides in the aquatic environment: a review

https://doi.org/10.1016/S0160-4120(03)00176-4 Get rights and content

Abstract

Organic booster biocides were recently introduced as alternatives to organotin compounds in antifouling products, after restrictions imposed on the use of tributyltin (TBT) in 1987. Replacement products are generally based on copper metal oxides and organic biocides. This ban has led to an increase in alternative coating products containing the above biocides. The most commonly used biocides in antifouling paints are: Irgarol 1051, diuron, Sea-nine 211, dichlofluanid, chlorothalonil, zinc pyrithione, TCMS (2,3,3,6-tetrachloro-4-methylsulfonyl) pyridine, TCMTB [2-(thiocyanomethylthio) benzothiazole], and zineb. Since 1993, several studies have demonstrated the presence of these biocides in European coastal environment as a result of their increased use. More recently, the presence of these biocides was also revealed in waters from Japan, United States, Singapore, Australia and Bermuda. This paper reviews the currently available data on the occurrence of these biocides in the aquatic environment. Some data dealing with the environmental fate, partitioning, behaviour and risk assessment of antifouling paint booster biocides are also reported in order to discuss the detected levels of contamination.

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

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