ICES Journal of Marine Science, 55: 34–43. 1998 Tributyltin inputs to the North Sea from shipping activities, and potential risk of biological effects Ian M. Davies, Susan K. Bailey, and Melanie J. C. Harding Davies, I. M., Bailey, S. K., and Harding, M. J. C. 1998. Tributyltin inputs to the North Sea from shipping activities, and potential risk of biological effects. – ICES Journal of Marine Science, 55: 34–43. The mechanisms leading to an annual input of tributyltin (TBT) to the North Sea from shipping are discussed. It is estimated that the gross annual input of TBT to the North Sea was 68 tonnes. A simple numerical model of the North Sea has been applied to the input data, and indicates that the greatest risk of biological effects of TBT from commercial vessels would be expected in areas of the south-eastern North Sea (NSTF Areas 4, 5), and off eastern England (Area 3ii). Low intensity of impact was indicated in the northern (Areas 1, 2, 3i) and north-central (Area 7i) North Sea. The sensitivity of the model output to variations in critical parameters of the behaviour and inputs of TBT are discussed, and are found to have minor effects on the overall conclusions. The estimates of relative risk of biological effects from TBT broadly reflect the impacts observed in dogwhelks (Nucella lapillus L.) in North Sea coastal areas. ? 1998 International Council for the Exploration of the Sea Key words: tributyltin, marine modelling, inputs, effects, dogwhelk, Nucella. Received 8 December 1995; accepted 17 January 1997. I. M. Davies, S. K. Bailey, and M. J. C. Harding: SOAEFD Marine Laboratory, PO Box 101, Victoria Road, Aberdeen, AB11 9DB, Scotland, UK. Correspondence to I. M. Davies: fax: +44 1224 295511; email: [email protected]. Introduction Since the introduction by several North Sea states of statutory controls on the use of tributyltin (TBT) compounds in antifoulants on small vessels and in mariculture, the major remaining use of TBT in the sea has been for the protection of large vessels. Field studies around harbours (e.g. Bailey and Davies, 1988) and major shipping routes (e.g. Ten Hallers-Tjabbes et al., 1994) have indicated that TBT from shipping can cause significant biological effects in sensitive species. TBT compounds from shipping may enter the environment in five ways: (a) at the time of ship construction, (b) when vessels are stationary in port (static leaching), (c) when vessels are under way at sea (dynamic leaching), (d) when vessels are in dry dock for repair and maintenance, including repainting, (e) when vessels are scrapped. These inputs will be unevenly distributed over the North Sea, and will be subject to differing degrees of 1054–3139/98/0100034+10 $25.00/0/jm970275 dispersion and dilution according to the hydrographic characteristics of various areas. For example, in the middle of the North Sea the main inputs will be from vessels on passage; however, the receiving waters in this area are slow moving. The faster moving water in the southern North Sea and the Channel has more traffic and harbours than other parts of the North Sea, and might receive greater inputs of TBT. The interactions between TBT and water fluxes may therefore lead to different intensities of effects on organisms around the coasts of the North Sea. To provide a framework to assist in the interpretation of a study of the impact of TBT on dogwhelks on the coast of the North Sea (Harding et al., 1992), an estimate has been made of the releases of TBT at that time from large vessels in various phases of their operation (on passage, in port, undergoing refit, etc.), as sources of TBT to the North Sea. These estimated inputs have been partitioned geographically between sea and coastal areas, and incorporated in a box model of the circulation of the North Sea to provide indications of the relative risk in these areas of biological effects from TBT from shipping. The sensitivity of the estimates of ? 1998 International Council for the Exploration of the Sea Tributyltin inputs to the North Sea 35 Table 1. Maximum inputs of TBT to the North Sea from individual states, based on the percentage of world trade entering each state (Stopford, 1988; A Milne, pers. comm.). State UK France Belgium Netherlands Germany Denmark Finland Sweden Norway Imports (M t) Percentage of world trade TBT input (t) 101 94 66 229 81 30 31 48 16 2.91 2.71 1.90 6.60 2.33 0.86 0.89 1.38 0.46 34.93 32.51 22.82 79.19 28.01 10.37 10.72 16.60 5.53 696 20.04 240.68 relative degrees of contamination to the assumptions inherent in the model is explored. The outputs from the box model are expressed as a ranking of the risk of biological effects in various sea areas. Little weight is given to the absolute values of the estimates of concentration of TBT in the sea water, as some of the environmental processes affecting TBT concentrations (e.g. interactions with solids) are not included in the model. However, the estimates are used to give an indication of relative risk of effects, for comparison with results of a broad-scale survey of imposex in dogwhelks (Harding et al., 1992). Estimation of the input of TBT to the North Sea from commercial shipping Global input of TBT resulting from shipping activities A first approach to estimating the annual input of TBT to the North Sea from commercial shipping may be made from consideration of the total global usage of TBT, and the proportion of global seaborne trade that passed through the North Sea. The amount of TBT in paint produced each year is taken as an estimate of the annual quantity lost from shipping. The total quantity of marine paint produced annually was approximately 25.106 l, of which about 80% was TBT-based (A. Milne, pers. comm.), i.e. approximately 20.106 l of TBT based paint produced annually. As the specific gravity of paint is about 1.5 g cm "3, this equates to approximately 30 000 t of paint. The average TBT content of marine paints was about 4%, and therefore approximately 1200 t of TBT was applied annually to ships’ hulls. In 1984, the volume of global seaborne imports was 3470 t#106 t, of which 20% passed through the North Sea (Stopford, 1988). On this basis, the maximum amount of TBT that might be released into the North Comment 82.7% of total of 122 M t of imports 50% of total of 197 M t of imports Assuming leakage from Baltic As above Sea from shipping may be estimated as 240 t (20% of 1200 t), and this figure may be roughly partitioned between states in proportion to their volumes of maritime trade (Table 1). This estimate of 240 t must be considered as a maximum value, against which to view the more detailed assessment below. Estimates of TBT inputs from specific sources A more detailed estimate of the input of TBT from shipping to the North Sea can be obtained by consideration of the various input mechanisms individually. The total input estimated by this method should not exceed 240 t. From ship building and dry-docking The annual production of paints containing 1200 t of TBT will be used on the hulls of new vessels, and on older vessels during dry-docking. The data for the following calculations were obtained from Stopford (1988). (i) From ship building. 630 million (M) dead weight tonnage (DWT) of shipping was used worldwide. The life expectancy of these ships was about 25 yr, so to replace the lost tonnage required 25 M DWT of shipping to be built each year. The majority (70%) was built in Japan and Korea, and only approximately 15% in the whole of Europe. The only significant builders along the North Sea coast were in Denmark and Germany, which accounted for around 25–30% of the total ship building in Europe. Typical periods between dry-docking were 2–2.5 yr, so 250 M DWT of shipping were dry-docked each year. New building (25 M DWT) was therefore about 10% of the total dock activity, i.e. used 120 t of TBT. It is estimated that perhaps 1% might be expected to be lost to the environment in solution (i.e. 1.2 t). The maximum 36 I. M. Davies et al. amount of TBT lost in all European waters was therefore 15% of this (i.e. 0.18 t), 0.05 t of which would be in the North Sea. (ii) Losses from dry docking activities. Each year, 25 M DWT of shipping (10% of the total trade) were drydocked in Northern Europe. Loss of TBT during dry docking will arise from hull washings/scrapings, and the over-spray of new paint material. The latter is considered to be a very small proportion of the total applied, particularly as it is in the economic interest of the yard to keep such losses to a minimum. It is likely that losses from washing/scraping co-polymer paints were also small. Much of the depleted paint would have degraded and been washed off during the useful life of the coating and high pressure hosing was normally sufficient to remove slime films and the remaining degraded surface down to sound paint, removing little material that contained high concentrations of TBT. This would not have been the case a number of years previously, when it was necessary to scrape off relatively large amounts of flaking free-association paints to obtain a sound base for re-painting. In addition, some shipyards actively took precautions to prevent contaminated water and chippings from the bottom of the dock from entering adjacent waterways. It is therefore concluded that the losses from dry docks would have been small. The shipping undergoing treatment in dry docks in Europe each year would use around 48 t TBT, of which it is estimated (as above) that approximately 1% (0.48 t), were lost in solution to the environment. By comparison, Harris et al. (1991) estimated that although a Naval Dockyard discharged up to 1 t of TBT annually to the Tamar estuary, it made a relatively small contribution to the input of TBT in solution, which was dominated by leaching from hulls. (b) From dynamic leaching The wetted area of the world fleet was approximately 60 M m2 (A. Milne, pers. comm.), and vessels typically spent approximately 250 days sailing (68.5%) and 115 days stationary each year (Stopford, 1988). If the dynamic leaching rate of TBT from hull antifoulants is taken to have been approximately 4 ìg cm "2 d "1 (Waldock, 1986), approximately 600 t of TBT would have been leached from vessels under passage to the world seas. However, the average passage distance on the high seas is around 4000 miles, whereas a typical passage distance in the North Sea is only about 400 miles. Therefore, as only 20% of the cargo passed through the North Sea, and travelled over about 10% of the route miles, the annual leaching while on passage into the North Sea may be estimated as 12 t. (c) From static leaching Based upon calculations similar to the above, the input of TBT to the world seas resulting from static leaching Table 2. Estimated total annual input of TBT to the North Sea. Source New building Dynamic leaching Static leaching Dry dock Ship-breaking Total Input of TBT (t) 0.05 12.00 55.30 0.48 Negligible 67.83 (i.e. 5.6% of the total world usage of TBT) while vessels were in port was 276 t. As 20% of world trade was in the North Sea, 55.3 t of TBT would have been leached in North Sea ports (this is probably an upper estimate, since North Sea ports were generally very efficient and handled cargoes rapidly). (d) Ship-breaking Almost no ship-breaking was carried out in northern Europe (Stopford, 1988), therefore TBT losses through scrapping will be negligible. The estimated total input of TBT to the North Sea from the individual sources is therefore shown in Table 2. Some indication of the reasonableness of these calculations can be obtained by considering that the sum of the estimated losses of TBT from the world fleet when static (276 t) and the loss when on passage (600 t) is 73% of the estimated world annual usage (1200 t) at that time. These two components are considered to make up the majority of the input to the environment from ship-related activities. Some of the shortfall may be accounted for by the incomplete removal of paint between repaintings, so that some ‘‘old’’ TBT will accumulate on the ships until scrapping. A relatively small change in the average leaching rate used in the above calculations, e.g. an increase from 4 to 5 ìg cm-2 d "1 (Waldock, 1986) could account for almost all the shortfall. It appears, therefore, that the calculations are, in broad terms, reasonably in balance. Significance of the estimated inputs to various areas of the North Sea The above calculations have been used to derive estimates of the inputs of TBT to the coastal waters of the North Sea, and also to the wider North Sea from vessels on passage. The biological impact of these inputs will have been primarily dependent upon the concentrations of TBT that were generated in the environment from these inputs. From Table 3, it appears that the largest input was to the Netherlands coast. The strongest *Half time=0.5 years. 1 Northern North Sea 2 3i Northeast UK 3ii Southeast UK English Channel 4 Netherland/Belgium 7i Central 7ii Central 5 Germany/Denmark Skagerrak 6 Norway Sea area On passage 6 18 201 373 524 825 21 29 201 79 59 0.60 0.35 2.04 3.91 5.66 26.11 0.00 0.00 7.65 7.49 1.27 0.03 0.08 0.94 1.75 2.46 3.87 0.10 0.14 0.94 0.37 0.28 0.63 0.43 2.98 5.66 8.12 29.98 0.10 0.14 8.59 7.86 1.55 0.50 0.50 0.03 0.01 0.18 0.19 0.60 0.45 0.36 0.20 0.36 Without With Shipping Total Outflow movements degradation degradation* (t) 106 m3 s "1 In harbour Local input (t) 0.75 0.35 0.30 0.30 0.20 0.17 0.35 0.20 0.10 0.10 0.50 0.00 0.08 0.00 1.00 0.00 8.02 29.92 59.40 37.97 30.81 25.66 Flushing From inflow time water (y) (t) 0.95 0.79 75.59 506.06 34.28 152.00 38.03 100.55 98.29 146.93 57.44 Rank 0.34 0.49 49.87 333.90 25.98 120.09 23.41 76.21 85.57 127.92 28.72 11 10 6 1 8 3 9 5 4 2 7 0.60 0.60 0.03 0.01 0.15 0.16 0.01 0.06 0.18 1.00 1.80 0.40 0.30 3.00 1.30 0.23 0.20 21.00 1.50 0.20 0.10 0.10 0.57 0.66 0.02 0.17 0.73 0.76 0.00 0.13 0.76 0.87 0.87 Exp 0.63 0.43 2.98 5.66 8.12 29.98 0.10 0.14 8.59 7.86 1.55 0.80 0.72 75.59 432.05 41.14 167.21 8.39 74.96 102.87 16.64 6.95 0.46 0.48 1.18 71.29 30.04 126.73 0.00 9.37 77.96 14.49 6.05 10 9 8 3 4 1 11 6 2 5 7 Total Without With (t) degradation degradation* Rank Concentration ngl "1 Flushing rates derived from observations Without With Outflow Flushing degradation degradation* 106 m3 s "1 time (y) Concentrations ngl "1 Flushing rates derived from modelling Table 3. Model of relative concentrations of TBT in various areas of the North Sea, based on flushing rates derived from modelling and from observation (ICES, 1983). 38 I. M. Davies et al. 62°N 1 60° 6 58° 2 3' 56° 7' 7" 5 54° 3" 4 52° 50° 100 m contour 48° 6°W 4° 2° 0° 2° 4° 6° 8° 10°E Figure 1. Subdivision of the North Sea used in this report, from ICES (1983). impacts might, therefore, be expected in this area. However, this approach disregards a range of hydrographic and chemical factors, such as the volume of the receiving sea water, its rate of advection away from the input area, and the degradation of TBT in sea water that took place after release. Tributyltin inputs to the North Sea 0.6 0.7 39 1.8 1 0.3 0.3 0.03 0.3 2 6 0.6 3' 1.0 7' Sk 0.8 0.01 0.01 0.18 0.02 7" 0.06 0.01 3" 5 0.04 0.01 0.12 4 0.15 Figure 2. Summary diagram of observed exchange pattern between North Sea areas. Estimated advective fluxes between boxes in 106 m3 s "1 (turbulent exchange indicated by dashed arrows between boxes). A preliminary approach to assessing the relative TBT contamination status (and hence risks of biological effects in sensitive organisms) of areas in the North Sea has been made using a simple box model of water circulation in the North Sea, and exchange with the North Atlantic and Baltic Sea (Fig. 1). In ICES (1983) the author(s) present a model, which treated the North Sea as being divided into nine boxes (plus the Skagerrak and the English Channel), included information on the flushing times of the boxes, and described the general 40 I. M. Davies et al. Table 4. Effects of variation of the degradation half-time of TBT between 2.0 and 0.2 years on the ranking of sea areas. Half-time 2.0 yr Area 1 Northern North Sea 2 3i Northeast UK 3ii Southeast UK English Channel 4 Netherlands/Belgium 7i Central 7ii Central 5 Germany/Denmark Skagerrak 6 Norway 10 9 6 1 5 2 11 4 3 7 8 1.0 yr 0.5 yr Rankings 10 9 7 1 5 2 11 4 3 6 8 10 9 8 3 4 1 11 6 2 5 7 0.2 yr 9 8 10 5 3 1 11 7 2 4 6 pattern of water movement produced from both modelled and observed advective fluxes between the boxes. (Fig. 2). This simple model has been used to investigate the possible relative significance to the areas of the North Sea of the inputs estimated above. The inputs from vessels in harbour in each country were assigned to the appropriate boxes in the model (Table 3). The input to the Skagerrak arose from trade to Sweden and Finland and initially appears likely to be an underestimate, as there was additional trade to countries bordering the south and east of the Baltic. However, TBT released from vessels in the Baltic proper, and further north, was unlikely to enter the Skagerrak or North Sea. The mean residence time of near-surface water in the Baltic proper is of the order of 25 yr, and so the great majority of TBT released in Baltic harbours would degrade before it was transported to the North Sea. It is therefore likely that the input figures used in the model are over-estimates of the input from shipping in Baltic harbours. The annual input from dynamic leaching (arising from vessels on passage) was estimated as proportional to the intensity of shipping movements in the various areas of the North Sea. Collated annual data on shipping movements are not readily available, and therefore data were extracted from the Atlas of the Seas Around the British Isles (MAFF, 1981). These data cover most of the North Sea and approaches, for a single period in 1976 (checked against periods in 1977–1979). In areas for which no data were available (the eastern North Sea north of the German Bight), intensities were assumed to be proportional to the volumes of trade in adjacent countries. In this way, it was possible to distribute the input from ships on passage between the boxes in the model to reflect the distribution of shipping movements. For reasons discussed above, inputs to the Baltic from vessels on passage in the Baltic are unlikely to contribute to TBT inputs to the North Sea. However, the omission of any consideration of inputs from vessels on passage to eastern Baltic ports will result in an under-estimate of inputs to waters at the entrance to the Baltic (Skagerrak). This may serve to counterbalance the overestimate arising from the treatment of inputs from Swedish and Finnish harbours as arising within the Skagerrak. It is known that TBT degrades in the marine environment and a degradation half-life of 0.5 yr has initially been used in the model (Waldock et al., 1990). This value is of the order of those half-lives observed in aerobic sediment, rather longer than those in water, and shorter than those in anaerobic sediment. In applying this circulation model, the behaviour of TBT has been described in a very simple manner. TBT is treated as a degradable dissolved substance, and the water within each box in the model is considered to be well mixed. It is assumed that inputs to harbours enter the main body of the North Sea and therefore can be considered as having the same potential for environmental impact as direct releases to the open sea from vessels on passage. It is recognized that TBT interacts strongly with solids and accumulates in areas of finegrained sediment (Readman and Mantoura, 1990). Therefore the location of harbours (e.g. on the open coast, as opposed to in estuarine areas with muddy sediment) may have considerable influence on the proportion of the TBT from any particular harbour that reaches the open sea (Harris et al., 1991). However, the considerable number of harbours in the North Sea area may serve to reduce any geographical bias in the overall distribution of inputs arising from details of individual harbours. Consequently, the model may be able to indicate the relative degrees of contamination of large areas, but cannot describe details of distributions of TBT around particular harbours or shipping lanes. The concentration of TBT in each box is firstly calculated as the flux of TBT to the box from static leaching, and ships on passage, plus that advected in from neighbouring boxes, divided by the out-going advective flux of water. This concentration is then decreased appropriately to allow for the degradation of TBT during the residence time of water in the box. The TBT concentrations (Table 3) obtained from calculations based upon flushing rates derived from modelling (ICES, 1983) show the least contaminated areas to have been sub-divisions 1 and 2, in the northern North Sea, remote from large commercial harbours (other than Sullom Voe, Shetland). The most contaminated areas are identified as those off the east coast of England (Area 3ii), and off Belgium, the Netherlands and Germany (Areas 4 and 5) and the Skagerrak (Area S). Area 3ii received only a moderate input, but had only Tributyltin inputs to the North Sea 41 Table 5. Effects on the ranking of sea areas of variation in the assumed efficiency of transfer of TBT from harbours to the open sea between 100% and 2%, and also of the inclusion of estimated inputs from dry dock activities for losses of TBT of 0 and 50%. Transfer efficiency (%) 100 Sea area 50 2 Ranking 1 Northern North Sea 2 3i Northeast UK 3ii Southeast UK English Channel 4 Netherlands/Belgium 7i Central North Sea 7ii Central North Sea 5 Germany/Denmark Skagerrak 6 Norway 10 9 8 3 4 1 11 6 2 5 7 10 9 8 2 4 1 11 6 3 5 7 10 9 8 2 4 1 11 6 3 5 7 Table 6. Results of the ranking of the North Sea areas for risk of biological impact from the model, based on observed flushing times (ICES, 1983), and the measured effects on dogwhelks (imposex; Harding et al., 1992). Ranking 3i Northeast UK 3ii Southeast UK 4 Netherlands/Belgium 5 Germany/Denmark 6 Norway Skagerrak English Channel Modelled risk Observed impact 7 3 1 2 6 5 4 7 5 1 3 1 4 6 0 Conc ng l a small advective flux. The Areas 4 and 5 received much greater inputs, but also experienced a greater advective flow, which partially compensated for the input. The most surprising output from the model is the high concentrations in Areas 7i and 7ii. The advective flow out of the former is very small, while the latter receives a significant input from Area 4 to the south. If the same calculations are carried out using flushing times from observations (ICES, 1983), a different pattern emerges (Table 3). The main differences between the modelled and observed flushing times are that the observed times are considerably longer in Areas 3i, 3ii, 7i, and 7ii. In this case, relatively low risks of environmental impact are again predicted in Areas 1, 2, and 6, but now also in Areas 3i, 7i, and 7ii. The greatest risks are indicated in Areas 4, 5, and 3ii, and intermediate levels of risk in the Skagerrak and the English Channel. Area Losses due to dry docking activities (%) "1 0.5 0.5 1.2 71.3 30.0 126.7 0.0 9.4 78.0 14.5 6.1 50 Rank Conc ng l "1 Rank 10 9 8 3 4 1 11 6 2 5 7 0.7 0.7 1.5 92.7 39.1 173.2 0.0 12.7 107.1 20.1 8.4 10 9 8 3 4 1 11 6 2 5 7 Discussion The estimated concentrations of TBT in the modelled boxes are all greater than would be expected to be found for dissolved TBT in North Sea waters (Karbe, 1992) although Cleary (1991) reported concentrations of TBT in unfiltered sea water of up to 30 ng tin l "1 in subsurface samples, and 4–75 ng tin l "1 in the surface microlayer. Quantitative comparisons of this nature may be misleading. The model does not discriminate dissolved or particulate-borne TBT, nor can it highlight local elevations of TBT concentrations in water, as have been found at sources of TBT such as harbours or marinas (Langstone and Pope, 1995). The results are not comparable to individual measured values of TBT concentrations in the different parts of the water column. Such observations are better addressed through other modelling techniques, which can include interactions of TBT with particles, and other processes (e.g. Harris et al., 1991). The absolute concentrations derived from the current model should not therefore be considered important, but the results may indicate the relative risk of biological effects over large areas. In general, both models (Table 3) highlight areas 3ii (English coastline) and 4 (Netherlands/Belgium coastline) as those likely to have shown the greatest TBT concentrations in the water, and therefore with the highest potential risk to many marine organisms. Area 5 (German/Danish coastline) and the Skagerrak were the areas with the next highest predicted risk, from both the observed and modelled flushing rates. To explore the robustness of the results of the modelling, the sensitivity of the output to the values of some of the important parameters of the model was investigated. 42 I. M. Davies et al. Firstly, a degradation half-life of 0.5 yr for TBT (Waldock et al., 1990) was used in the calculations. TBT has an affinity for particulate matter, resulting in sediments being the major reservoir for TBT (Langstone and Pope, 1995). Very high degradation rates of dissolved TBT (7–15 d, Seligman et al., 1986) were considered inappropriate, and therefore a lowest half-life of 0.2 yr was adopted. The effects on the relative risk of biological effects of varying the half-life of TBT between 0.2 and 2 yr are shown in Table 4. While some areas do change in relative risk, the general pattern of risk is not greatly dependent upon the assumed half-life of TBT. Secondly, it was assumed that TBT released in harbour areas was as available to the open sea as TBT released directly from vessels on passage. As discussed above, the affinity of TBT for particles will cause a proportion of the TBT to have been retained within harbours and estuaries. The effect on the ranking of sea areas of varying the assumed efficiency of transfer of TBT from harbours to more open sea areas between 100% (as in the initial model results, Table 3) and 2%, is shown in Table 5. It can be concluded that, although the assumed efficiency of transfer affects the estimated TBT concentrations, the ranking of the individual sea areas is not affected. Thirdly, it has been assumed that the leaching rate of TBT from stationary vessels is equal to that from vessels on passage. Dynamic leaching tests showed 5–10 ìg cm "2 d "1 leaching rate for copolymer paints with a proposed manufacturers leach rate of approximately 1 ìg cm "2 d "1 (Waldock, 1986). It is likely that leaching rates are greater when vessels are underway, although direct measurement is difficult (Schatzberg, 1990). Leaching rates have been estimated from experiments to range from 0.11–6.75 ìg TBT cm "2 d "1 depending on the type of paint (conventional or copolymer) and the length of immersion in aerated sea water (Anderson and Dalley, 1986). Other studies (Waldock, 1986) using a constant flow of water over a 2–3 mo period showed leaching rates of 4–5 ìg cm "2 d "1, illustrating the variability of leaching rates in the literature. Indeed, Harris et al. (1991) used a leaching rate of 0.1 and 0.3 ìg cm "2 d "1 when modelling the Tamar estuary, and acknowledged that this may be as much as an order of magnitude too low. Literature values for leaching rates are therefore rather variable. If the leaching rate is lower in harbours, this can be considered equivalent, so far as the model is concerned, to a reduction in the apparent transfer efficiency of TBT from harbours to the open sea. As indicated above, variation over a wide range of values of transfer efficiency (100–2%), equivalent to varying static leaching rate from 4–0.1 ìg cm "2 d "1, has little effect on the conclusions from the model. Finally, the losses to the environment from drydocking were considered to be insignificant (0.48 t), and were omitted from the modelling. It may be that this is an under-estimation of the actual losses, and the sensitivity of the modelling results to this parameter was therefore investigated. Dry docks are generally situated in port areas and the distribution of inputs of TBT from dry docks may therefore be modelled in the same way as the inputs from vessels in port, i.e. in proportion to the distribution of seaborne imports between countries. It is then possible (Table 5) to calculate the effect of varying the assumed percentage loss of TBT from dry docks from 0% (as in the initial model) to 50%. Losses of 50% increase the calculated concentrations of TBT, but have no effect on the ranking of the sea areas. It appears therefore that uncertainty in the scale of input of TBT from dry docks has no effect on the conclusions of the model. It may be concluded that the main simplifying assumptions concerning the inputs and behaviour of TBT do not greatly affect the general conclusions from the model. The relative risk of biological effects of TBT predicted by the model have been compared with the results of a broad study of the biological effects of TBT around the North Sea (Harding et al., 1992). These authors studied imposex (the development of male sexual characteristics in female dogwhelks, Nucella lapillus, in response to TBT exposure, Bryan et al., 1986) around the coastline of the North Sea. The Vas Deferens Sequence Index (VDSI, the stage of development of the male sexual organs, Gibbs et al., 1987) was measured. The results allowed each population examined to be classified as unlikely to show any reduction in reproductive capacity (VDSI <4); or as populations with higher impact of TBT, a proportion of sterile females and reduced reproductive capacity (VDSI 4–6). For the purposes of comparison, the dogwhelk sampling sites were grouped using the same geographical boxes as in the model. The percentage of dogwhelk sampling sites in each area at which the dogwhelks showed VDSI values of 4–6 was calculated, and the percentages ranked and compared to the results of the input model (Table 6). The predominantly offshore areas 1, 2, 7i and 7ii were not sampled for dogwhelks, and are therefore excluded. In broad terms, the actual measured biological effect mirrors the predicted areas of highest risk biological effect from TBT from derived shipping. There are two areas where the results differ, area 3(ii) along the English coast, and area 6 the western Norwegian coast. In area 6, the majority of the sites were chosen to investigate the extent of TBT contamination in harbours, 8 out of the 12 sites sampled in this area were from busy harbours. In this way, the sampling may have been biased and over-estimated the general Tributyltin inputs to the North Sea extent of TBT contamination along the coastline. The imposex results in area 3(ii) were based on relatively few samples. Conclusions 1. An assessment is presented of the distribution of inputs of TBT to the North Sea from shipping activities. 2. Combination with a simple box model of water circulation in the North Sea allows prediction of relative risk of biological effects caused by TBT in different areas of the North Sea. 3. In broad terms, the predicted relative risks reflect the observed distribution of effects in Nucella lapillus. Acknowledgements The data used in the calculations of inputs were compiled by Mr A. Milne, formerly of Courtaulds NCT, and Dr W. 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