Long-term temporal trends (1992–2008) of imposex status associated with organotin contamination in the dogwhelk Nucella lapillus along the Icelandic coast

Using the dogwhelk Nucella lapillus as a biomonitor, we evaluated the organotin contamination along the Icelandic coast over nearly two decades. In 2008, adult dogwhelks collected from 30 locations were examined for imposex status. In 2009, tissue concentrations of six organotin species in dogwhelks from 16 of the 30 locations were analysed using gas chromatography–mass spectrometry. Tributyltin was the most predominant residue ranging from 2.07 to 70.38 μg kg⁻¹ dw, while triphenyltin was also detected at concentrations up to 22.79 μg kg⁻¹ dw. Higher total organotin concentrations and imposex indices were observed at locations near large harbours (Reykjavík and Hafnarfjörður). By comparing the current imposex results with those of previous surveys (1992–2003), we found that recovery was slow near the large harbours, but more apparent near the smaller harbours. We also observed a notable increase in imposex at several northwest sites implying incessant input of organotins.     

Imposex levels in the dogwhelk Nucella lapillus (L.)--continuing improvement at high latitudes

In 1990, restrictions on the use of tributyltin (TBT)-based antifouling paints were implemented in Iceland. A previous study showed that the level of imposex in the dogwhelk, Nucella lapillus, in Icelandic waters had decreased significantly between 1992 and 1998. In this study, we repeated the survey on imposex in N. lapillus at 33 locations from the Icelandic coast in 2003. The results indicated that both Vas Deferens Sequence Index (VDSI) and Relative Penis Size Index (RPSI) had further declined in 13 locations since 1998. Among these 13 sites, RPSI was reduced to zero in five cases. While improvements from 1992/1993 to 1998 were seen in reduced levels of imposex near both large and small harbours, the pattern from 1998 to 2003 was somewhat different, with improvement mainly observed near smaller harbours. No significant changes in imposex levels near larger harbours occurred over this period. Although the imposex levels still remain high near the large harbour complexes in Reykjavík and Hafnarfjörður, it is evident that regulations, including the use of less toxic antifouling paints and community action, have lead to substantial improvements in the marine environment of Iceland. International Maritime Organisation’s ban on the application of TBT after 2003 is apparently necessary to allow further improvements in larger harbours. The environmental effects of new antifoulants replacing TBT need to be further evaluated.     

Imposex levels in the dogwhelk Nucella lapillus (L.)—continuing improvement at high latitudes

In 1990, restrictions on the use of tributyltin (TBT)-based antifouling paints were implemented in Iceland. A previous study showed that the level of imposex in the dogwhelk, Nucella lapillus, in Icelandic waters had decreased significantly between 1992 and 1998. In this study, we repeated the survey on imposex in N. lapillus at 33 locations from the Icelandic coast in 2003. The results indicated that both Vas Deferens Sequence Index (VDSI) and Relative Penis Size Index (RPSI) had further declined in 13 locations since 1998. Among these 13 sites, RPSI was reduced to zero in five cases. While improvements from 1992/1993 to 1998 were seen in reduced levels of imposex near both large and small harbours, the pattern from 1998 to 2003 was somewhat different, with improvement mainly observed near smaller harbours. No significant changes in imposex levels near larger harbours occurred over this period. Although the imposex levels still remain high near the large harbour complexes in Reykjavík and Hafnarfjörður, it is evident that regulations, including the use of less toxic antifouling paints and community action, have lead to substantial improvements in the marine environment of Iceland. International Maritime Organisation’s ban on the application of TBT after 2003 is apparently necessary to allow further improvements in larger harbours. The environmental effects of new antifoulants replacing TBT need to be further evaluated.     

Butyltin compounds,sterility and imposex assessment in Nassarius reticulatus (Linnaeus, 1758), prior to the 2008 European ban on TBT antifouling paints,within Basque ports and along coastal areas

Levels of imposex (superimposition of male characters, upon females) and the presence of sterile females are assessed in the gastropod Nassarius reticulatus (L.), at 35 locations in the Basque Country. At 18 of these localities, organotin bioaccumulation (tributyltin (TBT); dibutyltin; monobutyltin) was evaluated, using isotope dilution GC–ICP–MS. Higher imposex levels and TBT body burden were found in confined harbours, with large vessel traffic or the presence of an offshore fleet. The highest values were found for the port of Pasaia, near to a shipyard (a relative penis size index of up to 92%, and TBT body burden up to 405 ng g^?1 – given on a dry weight basis as Sn). Imposex effects were evaluated also in parasitized females, at some of the sampling sites. The percentage of presence of c-type Vas Deferens sequence stages (i.e., with vas deferens beginning at the oviduct opening) was higher in parasitized females. In turn, there was an absence of highly convoluted oviduct in parasitized females.     

Contaminants in molting long-tailed ducks and nesting common eiders in the Beaufort Sea

In 2000, we collected blood from long-tailed ducks (Clangula hyemalis) and blood and eggs from common eiders (Somateria mollissima) at near-shore islands in the vicinity of Prudhoe Bay, Alaska, and at a reference area east of Prudhoe Bay. Blood was analyzed for trace elements and egg contents were analyzed for trace elements, organochlorine pesticides, polychlorinated biphenyls, and polycyclic aromatic hydrocarbons. Except for Se (mean=36.1 microg/g dry weight (dw) in common eiders and 48.8 microg/g dw in long-tailed ducks), concentrations of trace elements in blood were low and, although several trace elements differed between areas, they were not consistently higher at one location. In long-tailed ducks, Se in blood was positively correlated with activities of two serum enzymes, suggestive of an adverse effect of increasing Se levels on the liver. Although common eiders had high Se concentrations in their blood, Se residues in eggs were low (mean=2.28 microg/g dw). Strontium and Ni were higher in eggs near Prudhoe Bay than at the reference area, but none of the other trace elements or organic contaminants in eggs differed between locations. Concentrations of Ca, Sr, Mg, and Ni differed among eggs having no visible development, early-stage embryos, or late-stage embryos. Residues of 4,4'-DDE, cis-nonachlor, dieldrin, hexachlorobenzene, oxychlordane, and trans-nonachlor were found in 100% of the common eider eggs, but at low concentrations (means of 2.35-7.45 microg/kg wet weight (ww)). The mean total PCB concentration in eggs was 15.12 microg/kg ww. Of PAHs tested for, residues of 1- and 2-methylnaphthalene and naphthalene were found in 100% of the eggs, at mean concentrations of 0.36-0.89 microg/kg ww.     

The significance of imposex levels and TBT contamination in the red whelk, Neptunea antiqua (L.) from the offshore Irish Sea

The extent to which open seas and oceanic waters have been contaminated by TBT is unclear since most sampling programmes have concentrated on inshore areas, particularly near harbours. Accordingly, the red whelk, Neptunea antiqua L. (Mollusca: Prosobranchia), a sublittoral and dioecious prosobranch species, was selected to investigate the potential effects of TBT-induced imposex in the central western Irish Sea. The presence of imposex was noted in > 90% of all female whelks that were examined on a monthly basis over a 12-month period. However, the proliferation of the vas deferens was not considered severe enough to affect the reproductive capabilities of the population. Low concentrations of butyltins were detected in the soft tissues of all whelks examined, ranging from 0.009 to 0.112 microg g(-1) Sn dry wt There was no significant correlation between the documented imposex stages and total butyltin contamination, indicating that the species is not a reliable bioindicator species of the effects of this contaminant.     

Organotins (TBT and DBT) in water, sediments, and gastropods of the southern Venice lagoon (Italy)

The release of tributyltin (TBT) from maritime traffic represents one of the main problems of direct, diffuse, and continued contamination of the marine environment. In the present survey, the concentrations of TBT and dibultytin (DBT) in brackish waters, sediments, and the gastropods Nassarius nitidus were evaluated in order to estimate the contamination of the southern part of the Venice lagoon. TBT and DBT were determined by GC-MS/MS. Recent contamination of TBT was found in brackish waters near marinas, whereas the highest concentrations of TBT and DBT were observed in surface sediments at dockyards and harbours. High content of organotin in the gastropods sampled near the dockyards, harbours, and marinas showed a mobilisation from the sediments through the food web. The present study allowed assessment of whether, despite the ban on the use of TBT paints, waters, sediments, and biota were still being contaminated by organotin compounds in the southern Venice lagoon.     

Organotin compounds in seawater and Mytilus galloprovincialis mussels along the Croatian Adriatic Coast

In this work, data on the level of organotin compounds (OTCs) in seawater and mussels collected along the entire Croatian Adriatic Coast are presented. The samples were collected in 2009 and 2010 at 48 locations representing different levels of maritime activities, including marinas, ports and reference sites. Butyltins (BuTs) were found in all analyzed samples, representing >97% of OTCs, and ranged from 0.46 to 27.98 ng Sn L(-1) in seawater and from <6 to 1675 ng Sn g(-1) in mussels. The results indicate a recent input of TBT, with the highest concentrations of BuTs found in the marinas. It appears that the Adriatic coast is still polluted with TBT despite the fact that TBT-containing antifouling paints have been banned in Croatia since 2008. It is questionable how much TBT pollution decreased since 2005, when a high incidence of imposex was established in the same area.     

Spatial and temporal changes of TBT pollution along the Portuguese coast: inefficacy of the EEC directive 89/677

Nucella lapillus imposex (superimposition of male characters onto prosobranch females) and organotin body burden were surveyed in the Portuguese coast in 1997 and 2000. Time comparisons of the available data on Nucella lapillus imposex in the Portuguese coast indicate a global increase of TBT pollution in recent years, revealing the inefficacy of the 1993 legislation that bans the use of TBT paints on small boats (<25 m). The absence or scarcity of the species inside harbours, which are the most polluted sites in Portugal, is probably a consequence of extinction due to female sterilisation by TBT.     

Inshore/offshore gradients of imposex and organotin contamination in Nassarius reticulatus (L.) along the Portuguese coast

Imposex and organotin (OT) tissue contamination of the netted whelk Nassarius reticulatus (L.) were assessed in the continental shelves around the main estuaries of the central coast of Portugal (Lisbon: Tagus estuary; Setúbal: Sado estuary) and the main coastal lagoon in the Southern of Portugal (Faro: Ria Formosa). Pollution levels were higher in areas of more intense boat traffic and shipyard activities and imposex showed a clear decreasing gradient from the estuaries to the offshore, in relation to a similar gradient of tissue contamination by tributyltin. Remarkably, imposex was extensively spread over the adjacent continental shelves of Tagus and Sado estuaries. The current work shows that TBT pollution is undoubtedly a matter of concern not only for the above estuaries where harbours are implanted but also for the adjacent continental shelves, regardless the massive dilution of contaminants that may occur in these deeper areas.     

Optimisation of the Operation of an Electrochemical Process To Treat TBT‐contaminated Sediments on a Pilot Scale

Since at least three decades tributyltin had been commonly used in paint formulations to protect ship hulls and submersed surfaces from fouling. This has resulted in negative and Technology, effects to the marine environment due to its high toxicity towards non‐target organisms and to its accumulation in sediments, especially near point sources of pollution. Even if a ban of TBT for its application in anti‐fouling paints is enforced the problem of TBT‐contaminated sediments will remain for the coming years due to the low degradation rates of organotin in sediments. In this work an electrochemical process at a pilot scale to destroy TBT in sediments was investigated. Previous experiences at a laboratory and technical scale have demonstrated the potential of this process to electrolytically degrade organotin species in sediments. This article deals with the optimisation of the pilot plant performance in terms of organotin degradation and operation costs monitoring additionally the effect of the electrochemical treatment on other pollutants such as heavy metals, PCBs, and PAHs. The aim was to investigate by means of a parametric study the range of operating conditions required to destroy TBT down to concentrations lower than 100 μg/kg; to determine the influence of those parameters on the performance of the process; and to evaluate the operation costs associated to the process. It was determined that it was possible to destroy TBT down to 100 μg/kg at current densities in the range of 4.4 to 6.6 mA/cm² and chloride concentrations of least of 0.2 mol/L with operation costs of 13 to 18 EUR/m³.     

Responses of mud snails from low and high imposex sites to sex pheromones

Imposex, male secondary sexual characteristics in female snails, is a morphological indicator of sub-lethal exposure to organotin compounds. The relation between imposex and behavioral responses to sex pheromones was studied. Responses of snails to sex specific pheromones were determined in laboratory assays. Females and males from a low imposex site and females, imposex females and males from a high imposex site were tested. The snails from the low imposex site showed the expected strong behavioral dimorphism with females responding to male pheromone and males responding to female pheromone. In assays using snails from the high imposex site, female and imposex females showed no dimorphism in response to pheromones and males showed a relatively weak dimorphism. As there was no breeding or egg capsule deposition at the high imposex site, we conclude that even the morphologically normal snails were behaviorally and reproductively compromised.     

The contribution of urban runoff to organic contaminant levels in harbour sediments near two Norwegian cities

The main aim of the present study was to compare the quality of particle emissions (urban runoff and settling particles in rivers and harbours) to the quality of top-layer bed sediments, for two Norwegian harbours (Oslo and Drammen). A sub-aim was to investigate whether non-industrial urban runoff contributed to the organotin load of sediments, apart from leaching from ship hulls. Time-integrated samples of stormwater runoff were obtained in an innovative manner, by sampling man-holes in the stormwater system. Settling particles were sampled with sediment traps. The study focused on PAHs, PCBs and organotin compounds. Contaminant levels were generally a factor of 2-10 (PAHs) and 3-30 (TBT) lower in emitted riverine and runoff particles than in top-layer bed sediments, except for PCBs in Oslo harbour (only 20-30% lower). Significant levels of tributyltin (TBT; median 140mug/kg) were shown in runoff particles, showing that TBT can also be emitted via urban sources, since the sampled man-holes were not in areas where dry-docking activities take place. Possible land-based TBT sources include long-lasting house paint and use of TBT as PVC stabilizer and timber preservative. Since there are ongoing emissions into the two studied harbour areas, it is concluded that the addition of an actively sorbing capping material such as activated carbon might be the best remediation alternative.     

Organotin and total tin in coastal waters of Southwest England

Samples of seawater from sites along the southwest coast were collected during 1984 and analysed for total tin and organotin by flameless atomic absorption spectro-photometry. Organotin concentrations were below detection limits (0.10 μg l^?1 TBTO) at all marina sites, but higher concentrations were found in harbour waters, the highest value being 0.88 μg l^?1 TBTO at Plymouth (Sutton harbour). The fact that organotin levels may occasionally exceed some toxicological threshold concentrations suggests that biological water quality may sometimes be depressed.     

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in harbor sediments from Sea Lots, Port-of-Spain, Trinidad and Tobago

Concentrations of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were determined in nearshore marine surficial sediments from three locations in Trinidad. Sediments were sampled at Sea Lots on the west coast, in south Port-of-Spain Harbor, south of Sea Lots at Caroni Lagoon National Park, and on Trinidad’s east coast at Manzanilla. Total PCB concentrations in Sea Lots sediments ranged from 62 to 601 ng/g (dry weight {dw}), which was higher than at Caroni and Manzanilla, 13 and 8 ng/g dw, respectively. Total OCP concentrations at Sea Lots were ranged from 44.5 to 145 ng/g dw, compared with 13.1 and 23.8 n/g (dw), for Caroni and Manzanilla respectively. The concentrations of PCBs and of some OCPs in sediments from Sea Lots were above the Canadian interim sediment quality guidelines. To date, this data is the first report on the levels of PCBs and other organochlorine compounds from Trinidad and Tobago.     

Imposex in the indigenous Nassarius kraussianus (Mollusca: Neogastropoda) from South African harbours

Nassarius kraussianus populations in the Durban and Richards Bay harbours (along the eastern seaboard of southern Africa) and in the Knysna lagoon (southern Cape coast) showed imposex development, confirming bioavailability of tributyltin (TBT) in these waterways. Incidence of imposex (which ranged from 29% to 100%) and relative penis length of females (RPL; which ranged from 1.3% to 55.2%) were markedly variable among populations from different sites in each waterway, indicative of localised effects of TBT contamination. Shell length of the snails was apparently not correlated with contamination level, as assessed from imposex measurements. While population imposex features are easy to determine and often provide a sensitive biomarker of TBT exposure, the discussion outlines reservations when extrapolating these to general ecological situations. Additionally, this study represents the first published report on the topic for sub-Saharan, African harbours, some of which seem remarkably less affected than suggested for other world regions.     

Occurrence and distribution of microplastics in marine sediments along the Belgian coast

Plastic debris is known to undergo fragmentation at sea, which leads to the formation of microscopic particles of plastic; the so called ‘microplastics’. Due to their buoyant and persistent properties, these microplastics have the potential to become widely dispersed in the marine environment through hydrodynamic processes and ocean currents. In this study, the occurrence and distribution of microplastics was investigated in Belgian marine sediments from different locations (coastal harbours, beaches and sublittoral areas).Particles were found in large numbers in all samples, showing the wide distribution of microplastics in Belgian coastal waters. The highest concentrations were found in the harbours where total microplastic concentrations of up to 390 particles kg⁻¹ dry sediment were observed, which is 15-50 times higher than reported maximum concentrations of other, similar study areas.The depth profile of sediment cores suggested that microplastic concentrations on the beaches reflect the global plastic production increase.     

210Po and 210Pb variations in fish species from the Aegean Sea and the contribution of 210Po to the radiation dose

In recent years, there has been increasing interest in the significance of natural radionuclides, particularly (210)Po, in the marine environment. (210)Po, a naturally occurring alpha emitter, accumulates in marine organisms and reflects differences in their diets. In the literature, there is no data for (210)Po and (210)Pb activity concentrations for fish species on the Turkish coast of Aegean Sea. Therefore, in this study, multiple fish species were collected from six stations seasonally on the Turkish coast of Aegean Sea and were analyzed for their (210)Po and (210)Pb content. The (210)Po and (210)Pb concentrations in the fish samples were found to vary from undetectable levels to 499 ± 44 Bq kg(-1) dry weight (dw) and from 1.0 ± 0.3 Bq kg(-1) to 35 ± 4.0 Bq kg(-1) (dw), respectively. There were no significant differences in the activity concentrations of (210)Po and (210)Pb in fish samples between seasons (ANOVA, P>0.05). The highest dose contribution of (210)Po to humans was calculated to be 10,530 μSv year(-1).     

Metals contamination along the watershed and estuarine areas of southern Bohai Sea,China

Distributions and magnitude of metals in water, sediment and soil collected from the watershed and estuarine areas of southern Bohai Sea, were investigated. The largest dissolved concentrations of As, Cu and Zn in water were 347.70, 2755.00, 2076.00 μg/L, respectively, much higher than corresponding drinking water guidelines. The greatest concentrations of Cu, Zn, Cr, Ni, Pb, As and Cd in sediments were 1462.2, 1602.17, 196.43, 67.15, 63.54, 73.86 and 1.41 mg/kg, dw, respectively. The mean concentrations of Cu, Ni, Cd, Zn, Cr, Pb and As in soils were 24.67, 24.73, 0.14, 64.75, 56.52, 25.12 and 9.34 mg/kg, dw, respectively. Land use was confirmed to be an important factor of influence on soil metal concentrations. Metal contents along the watershed of Jie River were significantly greater than in other locations. The detection of metals in relatively high concentrations from different environmental matrices in this region indicates the necessity of further studies.     

Dioxin-like compounds in sediments from the Daliao River Estuary of Bohai Sea: distribution and their influencing factors

The concentrations, compositional profiles, and potential ecological risk of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) in sediments of the Daliao River Estuary were investigated. Total concentrations of PCDD/Fs, PCBs, and PCNs were in the range of 11.3-133.2 ng/kg dry weight (dw), 1 971-37 632 ng/kg dw and 33.1-284.4 ng/kg dw, respectively. The total TEQ values varied from 0.37 to 4.08 ng/kg dw, with the dominant contributions by PCDD/Fs, then by PCBs and PCNs. The spatial distributions of PCDD/Fs, PCBs and PCNs in the river estuary were much related to hydrodynamic conditions. The risk of contamination to the deeper sea was increased in the flood seasons. Moreover, our data confirmed that both organic matter in sediments and molecular properties of dioxin-like compounds were the factors which strongly influenced the partition behavior of these dioxin-like compounds between sediments and water phase in the estuarine zone.