Imposex and organotin concentrations in Buccinum undatum and Neptunea antiqua from the North Sea: relationship to shipping density and hydrographical conditions.

The presence and the development of imposex were investigated in the common whelk (Buccinum undatum) and the red whelk (Neptunea antiqua) from the open North Sea and the Skagerrak. Imposex development was related to levels of organotins in snails and in the fine fractions (< 63 microm) of the sediments they inhabit. The sampling locations were classified according to three levels of traffic densities of ships of > or = 100 gt per day passing within 15 Nautical miles of the sampling station, shipping levels being: high (> 10 ships day(-1)), intermediate (5--10 ships day(-1)), and low (< 5 ships day(-1)). Sampling stations were also classified according to presence or absence of a vertically stratified water column. In the snails the body levels of the butyltin metabolites MBT and DBT and the parent phenyltin compound TPT, were higher than those of TBT and PT metabolites. In the sediment, the parent compounds and the mono-substituted metabolites MBT and MPT were present in the highest concentrations. The highest body levels of all organotin compounds and the highest imposex indices for the common whelk were found at those locations in the Southern Bight and the German Bight that had a high shipping density as well as a homogeneously mixed water column during the whole year. At these locations sediment levels of organotins were also higher than at other sites. In contrast, the body levels of organotins were low and imposex was sometimes even completely absent in snails from stratified deep-water stations in the Skagerrak, despite a very high shipping density in the entrance area of the Baltic. In sediments from stratified locations with low or intermediate shipping densities, organotin compounds were below or close to their respective limits of detection. These stations were located in areas with a stratified water column during the whole year. The results can be explained by postulating a much higher resistance for dissolved organotins to migrate through a pycnocline. Organotins could only transgress through a pycnocline when adsorbed to settling particles that manage to transgress the boundary between layers. N. antiqua could only be obtained in sufficient numbers from deeper water stations, which almost all had a stratified water column. At stations where both snail species were obtained and imposex was present, the imposex index was higher in the red whelk. Hence N. antiqua seems to be the more sensitive species of the two. In the red whelk, imposex development increased with shipping density too, though in the smaller samples the trend was not significant. Average biota-sediment accumulation factors (BSAFs; normalised for lipid content in snails and TOC content in the fraction < 63 microm in sediments) for Buccinum ranged from 0.4 to 1.0 for butyltins and were similar to literature values reported for TBT in other marine species. Higher average BSAF values were found for phenyltins 1.5 (MPT) to 17 (TPT). The high values for TPT match the ranges expected from equilibrium partitioning concepts of persistent hydrophobic compounds. The ratio of live snails to the total number of live snails plus empty shells ranged between 2.5 and 93%. This parameter might be a useful indicator to compare past and present densities of populations of both species in different areas of the North Sea.

Levels of polybrominated diphenyl ether (PBDE) flame retardants in animals representing different trophic levels of the North Sea food Web.

The levels of individual PBDE congeners were investigated in the invertebrate species whelk (Buccinum undatum), seastar (Asterias rubens), and hermit crab (Pagurus bernhardus), the gadoid fish species whiting (Merlangius merlangus) and cod (Gadus morhua), and the marine mammal species harbor seal (Phoca vitulina) and harbor porpoise (Phocoena phocoena). These species are all important representatives of different trophic levels of the North Sea food web. All six major PBDE congeners detected (BDEs 28, 47, 99, 100, 153, and 154) are most prevalent in the commercial Penta-BDE formulation. There is no evidence for the occurrence of the Octa-BDE formulation in the North Sea food web, since its dominant congener, BDE183, was never detected. BDE209, the main congener (> 97%) in the Deca-BDE formulation, was detected only in a minority of the samples and always in concentrations around the limit of detection. Since BDE209 is often the major BDE congener in sediments from the area, the main reason for its low concentrations in biota from the North Sea seems to be a relatively low bioaccumulation potential. This can either be due to a low uptake rate of the very large molecule or a relatively rapid excretion after biotransformation. Since all invertebrates investigated are sentinel species, they are highly representative for the area of capture. The highest lipid-normalized concentrations of PBDEs in the invertebrates occurred near the mouth of the river Tees at the East coast of the UK. The geographical distribution of the PBDEs can be explained by the residual currents in the area. The direction of these currents differs between the summer and the winter season as a result of the presence or absence of vertical summer stratification of the deeper waters north of the Dogger Bank. Summer stratification results in the development of a density-driven bottom water current formed after the onset of vertical stratification of the water column in May leaving the UK coast near Flamborough Head toward the Dogger Bank. In winter, the residual currents run in a more southerly direction and follow the UK coastline. The distribution pattern of the PCBs and p,p'-DDE in the invertebrates was entirely different from that of the PBDEs, which could be expected, since the use of these organochlorines in western Europe peaked in the 1960s and 1970s but has been forbidden more than two decades ago, whereas the production and use of the penta-BDE formulation is of a more recent origin. The higher trophic levels of the North Sea food web were represented by the predatory gadoid fish species whiting and cod and the marine mammal species harbor seal and harbor porpoise. The lipid-normalized levels of the six major PBDE congeners in fish were similar to the levels in the invertebrates, but a biomagnification step in concentrations of generally more than an order of magnitude occurred from gadoid fish to marine mammals. Based on the limited number of samples, no differences could be observed between harbor seal and harbor porpoise. In summary, the results in three species of sentinel invertebrates from a network of stations covering a major part of the North Sea basin showed that the estuary of the river Tees at the UK East coast is a major source for tri- to hexa-PBDEs. Throughout the food-chain, the most marked increase in (lipid-normalized) levels of all six PBDE congeners occurred from predatory (gadoid) fish to marine mammals, agreeing with the transition from gill-breathing to lung-breathing animals. This has serious consequences for the route of elimination of POPs, since their elimination from the blood into the ambient seawater via the gill-membrane is no longer possible.

Imposex induction in laboratory reared juvenile Buccinum undatum by tributyltin (TBT).

Here we report a series of experiments on the development and occurrence of imposex in the common whelk, Buccinum undatum, under the influence of (chronic) exposure to butyltin compounds. The main objective of the experiments was to obtain more information about the effects of organotin compounds in the marine environment, which possibly relate to the reported decline of B. undatum in Dutch coastal waters. In these studies tributyltin (TBT) dose-dependently induced the development of male sexual organs in juvenile whelks. A TBT concentration >7 ng Sn/l induced imposex in juvenile whelks. Growth in TBT-exposed juvenile whelks was significantly reduced compared to the reference group at a nominal TBT dose ≥ 4 ng Sn/l in one of the exposure studies. After 5 years in the laboratory, egg-laying was only observed in reference aquaria. Thus, TBT might impair whelk reproduction through growth reduction. The results showed a sensitivity towards imposex development in different life-stages. Juveniles were the most sensitive, adolescent females also responded, but adult females did not respond to TBT exposure, although they dose-dependently increased their organotin (OT) body-burden when exposed. Environmental TBT during only the in ovo stage, did not result in an increased masculinisation compared to non-exposed developing whelks. Histological studies showed no sterilisation due to mechanical blockage of the (adult) female genital opening by sperm-duct tissue. Gonadal development in 2-year old juveniles was not observed. This implies that the differentiation of a penis and a vas deferens, which already occurred in the first few months after hatching, was not controlled by gonadal factors. No other sexual characteristics than those already visible with the eye were found. TBT inactivated CYP450 to its inactive form CYP420 in in vitro exposure studies with microsomal fractions of whelks. The studies have shown TBT to disrupt sexual development dose dependently in juvenile common whelks. TBT also dose dependently exerts an effect on enzymatic (CYP450) processes. Although no mechanical sterilisation was observed, reproduction might be impaired through growth reduction.