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In 2001, legislative measures were introduced in the UK to restrict usage of antifouling agents in small (<25 m) vessel paints to dichlofluanid, zinc pyrithione and zineb. This removed the previously popular booster biocides diuron and Irgarol 1051 from the market. To investigate the impact of this legislation, water samples were taken from locations where previous biocide levels were well documented. Results from analyses demonstrate a clear reduction in water concentrations of Irgarol 1051 (between 10% and 55% of that found during pre-restriction studies), indicating that legislation appears to have been effective. Although other booster biocides were screened for (chlorothalonil, dichlofluanid and Sea-Nine 211), they were below the limits of detection (<1 ng/l) in all samples. A survey of chandlers and discussions with legislative authorities supports these results and concurs the removal of Irgarol 1051 based paints from the market using simple regulations at a manufacturer level with little regulation at a retailer level.

Measurements of the stress imposed by a PSII inhibiting herbicide (Irgarol 1051) on the composition of a phytoplankton community was investigated by comparing chemotaxonomy, as determined by high performance liquid chromatography (HPLC), optical microscopy and analytical flow cytometry (AFC). Changes in community structure were induced in microcosms containing a natural marine phytoplankton community exposed to different concentrations of Irgarol 1051 (0.5 and 1.0 microgl-1). Microcosms were maintained under controlled laboratory conditions in semi-continuous culture over 120 h. Class-specific phytoplankton biomass (chlorophyll a) was estimated using CHEMTAX analyses of pigment concentrations. Microscopic identification and carbon content estimates were cross-correlated with CHEMTAX and also with AFC enumeration/size classifications of major phytoplankton groups. CHEMTAX-HPLC analyses and microscopy results demonstrated that prasinophytes and prymnesiophytes were the most affected groups following exposure to Irgarol 1051. The selective reductions in both classes as estimated by both techniques revealed similar trends. Results for chlorophytes and dinoflagellates showed these groups to be most tolerant to Irgarol 1051. Indeed, class-specific biomass for chlorophytes as determined by CHEMTAX and microscopy were correlated (R2=0.53) which demonstrated an increase in both abundance and carbon content following exposures to Irgarol 1051. Abundances of nanoeukaryotes as determined by microscopy afforded good agreement with results from AFC (R2=0.8), although for picoeukaryotes, abundances were underestimated by microscopy (R2=0.43). The relative performance of the selected techniques is discussed.

Characterisation of natural phytoplanktonic communities is currently being advanced through flow cytometry and high resolution pigment analyses. To date, toxicological methods to assess impacts of herbicides on natural phytoplankton populations are lacking. Here, we report the novel use of these techniques in combination to study changes in phytoplankton populations exposed to 2-methylthio-4-tertiary-butylamino-6-cyclopropylamino-s-triazine (Irgarol 1051), a herbicide used in antifouling paints. Flow cytometry results revealed that following a 72-h exposure to approximately 100 ngL(-1), eukaryote abundance was less than half that in the controls. High performance liquid chromatographic analyses of pigments demonstrated that 19'-hexanoyloxyfucoxanthin was selectively lost relative to the control. This carotenoid is specific to the prymnesiophytes which are key constituents of phytoplanktonic communities within temperate marine waters. Values of EC(50) (72 h) as low as 70 ngL(-1) were calculated from the selective reduction in this compound. Concentrations substantially exceeding this level have been reported in UK and other European coastal waters.

Variations in Irgarol 1051 concentrations in the UK's largest marina at Brighton were determined regularly over a period of one year. Aqueous concentrations ranged from <1 to 960 ngl(-1) with highest mean concentrations generally associated with berths for larger vessels and with the main channels. Temporally, highest concentrations were recorded in November through to January and were probably associated with maintenance of vessels in an adjacent boatyard. Elevated levels were also encountered at the beginning of the season, coinciding with the introduction of newly antifouled vessels. Increased concentrations also followed dredging, possibly through re-mobilisation of Irgarol 1051. No correlations were found between dissolved Irgarol 1051 concentrations and pH, temperature or salinity. With the exception of sporadically high concentrations recorded for water samples (probably taken in close proximity to recently antifouled vessels), concentrations rarely exceeded the no observed effect concentration for marine periphyton of 63 ngl(-1). Concentrations of Irgarol 1051 in sediments sampled from the marina ranged from <1 to 77 ngg(-1). Apparent distribution coefficients (K(d)) calculated from sedimentary and aqueous samples (collected simultaneously) are generally within the range of K(d)'s reported from laboratory experiments.

In the yachting sector of the UK antifouling market, organic biocides are commonly added to antifouling preparations to boost performance. Few data presently exist for concentrations of these compounds in UK waters. In this study the concentrations of tributyltin (TBT) and eight booster biocides were measured before and during the 1998 yachting season. The Crouch Estuary, Essex, Sutton Harbour, Plymouth and Southampton Water were chosen as representative study sites for comparison with previous surveys of TBT concentrations. Diuron and Irgarol 1051 were the only organic booster biocides found at concentrations above the limits of detection. Diuron was measured at the highest concentrations, whilst detectable concentrations of both Irgarol 1051 and diuron were determined in areas of high yachting activity (e.g. mooring areas and marinas). Maximum measured values were 1,421 and 6,740 ng/l, respectively. Lower concentrations of both compounds were found in open estuarine areas, although non-antifouling contributions of diuron may contribute to the overall inputs to estuarine systems. TBT was found to be below or near the environmental quality standard (EQS) of 2 ng/l for all samples collected from estuarine areas frequented by pleasure craft alone, but with much higher concentrations measured in some marinas, harbours and in areas frequented by large commercial vessels. Using the limited published environmental fate and toxicity data available for antifouling booster biocides, a comparative assessment to evaluate the risk posed by these compounds to the aquatic environment is described. TBT still exceeds risk quotients by the greatest margins, but widespread effects due to Irgarol 1051 and less so diuron cannot be ruled out (particularly if use patterns change) and more information is required to provide a robust risk assessment.

A study of the distribution of the 'booster' biocide 2-methylthio-4-tert-butylamino-6-cyclopropyl amino-s-triazine (Irgarol 1051) was carried out in the coastal waters of Bermuda. Irgarol 1051 concentrations (as determined by GC/MS) up to 590 ng l-1 have been measured within Hamilton Harbour. The data presented herein unequivocally demonstrate contamination of the coastal system of Bermuda by Irgarol 1051. Concurrently, TBT concentrations were measured and results indicate that levels are falling through legislated changes in antifouling treatments, from 220 ng l-1 in 1990 to < 20 ng l-1 (as Sn) by 1995, in the open water area of Hamilton Harbour. Concentrations of TBT immediately offshore from a boatyard were found to be > 600 ng l-1 (Sn), indicating continuing release due to painting operations and sediments in the area.