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.     

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.     

Occurrence and effects of organotins on adult common whelk (Buccinum undatum) (Mollusca, Gastropoda) in harbours and in a simulated dredging situation.

Transplanted common whelk (Buccinum undatum) (Mollusca, Gastropoda) accumulated fairly high levels of organotins (tributyltin (TBT) and triphenyltin (TPT)) during exposure in three harbours with different TBT contamination. This did not though lead to an increase in imposex frequency in the adult females studied. Simulating harbour dredging in an experiment using suspended sediment from one of the harbours only resulted in a low concentration of TBT in the tissues of the common whelk and subsequently no changes in the occurrence and degree of imposex. The common whelk seemed to receive the main part of TBT from the water column and the limited bioaccumulation in the experiment indicates that desorption of TBT from the suspended sediment was slow. After TBT has been totally banned, dredging of contaminated sediments will cause increased exposure of the biota to TBT. Due to slow desorption the increase may however, be slight and temporary to pelagic and epibenthic species unless the settled particles are resuspended.     

Organochlorine, Heavy Metal and Polyaromatic Hydrocarbon Pollutant Concentrations in the Great Barrier Reef (Australia) Environment: a Review

Past monitoring of heavy metals, organochlorine compounds and polyaromatic hydrocarbons (PAHs) has found that pollutant concentrations are generally low within the Great Barrier Reef Marine Park and World Heritage Area and are indicative of a relatively unpolluted environment. The exceptions are sites that are adjacent to human activity such as ports and harbours, urban centres and areas adjacent to intensive agricultural activity. These sites have elevated concentrations of a range of pollutants. Concentrations of dioxins have also been found to be elevated in marine park sediments. Elevated pollutant concentrations are generally the consequence of effluent discharge, urban stormwater, and agricultural and industrial runoff. However, a majority of Great Barrier Reef pollutant data are now dated, and contemporary information is required concerning the distribution and impact of pollutants in the Queensland marine environment. The utility of specialized monitoring tools such as biomarkers for tropical marine environments urgently needs to be examined. With this information, appropriate risk assessment and monitoring can be implemented and effective management strategies developed to protect tropical marine ecosystems including the Great Barrier Reef.     

Organic pollutants (PAHs, PCBs) in sediments from the Mar Piccolo in Taranto (Ionian Sea, Southern Italy)

Polychlorinated biphenyls (PCBs) and 17 parent polycyclic aromatic hydrocarbons (PAHs) were determined in surface sediments from nine stations in the Mar Piccolo of Taranto (Ionian Sea, Southern Italy). Total PAH concentrations ranged from 380 to 12,750 microg/kg d.w., while total PCB levels ranged from 2 to 1684 microg/kg d.w.; this values were higher than those found in others marine coastal areas of the Mediterranean Sea. For PAHs, low molecular weight/high molecular weight, phenanthrene/anthracene and fluoranthene/pyrene ratio were used for discriminating between pyrolitic and petroleum origin. Results showed that PAHs were mainly of pyrolitic origin. PCB and PAH levels in sediments were compared with Sediments Quality Guidelines (ERM-ERL, TEL-PEL indexes) for evaluation probable toxic effects on marine organism. Finally, ERM and PEL quotients were used to evaluate the degree to which chemicals exceed guidelines. Results suggest an ecotoxicological risk for benthic organisms mainly in the first inlet, where high concentrations of PCBs were found in sediments influenced by harbour activities.     

DDTs and other chlorinated organic pesticides and polychlorinated biphenyls pollution in the surface sediments of Keratsini harbour, Saronikos gulf, Greece

Sediment samples were collected from Keratsini harbour, Saronikos gulf, Greece and were analysed for chlorinated organic pesticides (DDTs, HCB, Lindane) and polychlorinated biphenyls (PCBs). High total DDTs values were detected in all the sediments samples ranging from 9.1 to 75.6 mug/g, dry weight. PCBs concentrations range from 47.8 to 351.8 ng/g. The results and especially the high concentrations of DDTs reflect the influence of the industrial and urban wastes in the pollution for the Keratsini harbour environment.     

Environmental recovery in Sydney Harbour,Nova Scotia: Evidence of natural and anthropogenic sediment capping

Contaminants were assessed in Sydney Harbour during baseline and three years of remediation of a former coking and steel facility. Concentrations of PAHs; PCBs; and lead measured in surface sediments indicate overall spatial distribution patterns of historical contaminants remains unchanged, although at much lower concentrations than previously reported due to natural sediment recovery. Recovery rates were in broad agreement with predicted concentrations; or in some cases lower, despite remediation at the Sydney Tar Ponds (STP) site. Contaminants showed little temporal variability, except for detection of significant increases in PAH concentrations during onset of remediation compared to baseline which represented a short term interruption in the overall long term natural recovery of sediments in Sydney Harbour. Recovery (via “capping”) was enhanced following recent harbour dredging activities where less contaminated outer harbour sediments were discharged into a confined disposal facility (CDF) required for a new container in the inner harbour.     

Organic pollutants (PAHs,PCBs) in sediments from the Mar Piccolo in Taranto (Ionian Sea,Southern Italy)

Polychlorinated biphenyls (PCBs) and 17 parent polycyclic aromatic hydrocarbons (PAHs) were determined in surface sediments from nine stations in the Mar Piccolo of Taranto (Ionian Sea, Southern Italy). Total PAH concentrations ranged from 380 to 12,750 μg/kg d.w., while total PCB levels ranged from 2 to 1684 μg/kg d.w.; this values were higher than those found in others marine coastal areas of the Mediterranean Sea. For PAHs, low molecular weight/high molecular weight, phenanthrene/anthracene and fluoranthene/pyrene ratio were used for discriminating between pyrolitic and petroleum origin. Results showed that PAHs were mainly of pyrolitic origin. PCB and PAH levels in sediments were compared with Sediments Quality Guidelines (ERM–ERL, TEL–PEL indexes) for evaluation probable toxic effects on marine organism. Finally, ERM and PEL quotients were used to evaluate the degree to which chemicals exceed guidelines. Results suggest an ecotoxicological risk for benthic organisms mainly in the first inlet, where high concentrations of PCBs were found in sediments influenced by harbour activities.     

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.     

Legacy contaminant bioaccumulation in rock crabs in Sydney Harbour during remediation of the Sydney Tar Ponds,Nova Scotia,Canada

Concentrations of PAHs, PCBs, metals and lipids in hepatopancreas of rock crabs (Cancer irroratus) were measured in Sydney Harbour (SH) for one year prior to remediation and three years of remediation of the Sydney Tar Ponds (STP), Nova Scotia. Low level concentrations of PCBs and metals were measured, although PAHs were mostly undetected. Metal concentrations showed little spatio-temporal variability, although highest concentrations of As, Cd and Cu were measured at reference stations furthest from the STP remediation site. Mercury concentrations were at least an order of magnitude lower than Canadian guidelines. Moderately elevated PCB concentrations were detected in crabs near Muggah Creek, but these were generally not higher than those measured during baseline. Despite remediation activities, current contaminant burdens measured in crabs were much lower than previously reported in other studies of crabs and lobster in industrial harbours in eastern Canada, due in part to natural recovery of SH sediments.     

Hydrocarbon contamination in sediments from urban stormwater runoff

This investigation showed that urban stormwater runoff provides a significant amount of petrogenic material to receiving waters and sediments. A characteristic hydrocarbon ‘fingerprint’ for sediments and particulate matter in the Hillsborough Reservoir, Hillsborough River and upper Hillsborough Bay was provided. Determination of source material for petroleum contamination in stormwater runoff and river sediment indicated that crankcase oil was a primary contributor to sediment hydrocarbon contamination. A comparison of sediment hydrocarbons with hydrocarbons from stormwater runoff showed that the most probable source of crankcase oil-like petrochemicals found in sediment was the stormwater runoff.A comparison of hydrocarbon composition in suspended particulate matter with that of accumulated bottom sediments in the reservoir, river and bay, during a non-storm period and rising tide showed no resuspension and upriver transport of petroleum contaminated bay sediment. No special influence of the bay upon the lower river was observed relative to hydrocarbon tracers, indicating that most contaminated sediment transport was downriver during storm events. Additional studies should be performed over various tidal cycles and storm events incorporating sediment cores, sediment grain size analysis and hydrocarbon characterization at more closely spaced stations near the river mouth to address adequately the question of specific hydrocarbon pollution sources, rate of petroleum influx and persistence of petrochemical contaminants in the sediment.     

Monitoring of organic contaminants in sediments from the Korean coast: Spatial distribution and temporal trends (2001-2007)

Spatial and temporal trends of organic contaminants in sediments along the Korean coast were estimated through a nationwide environmental monitoring program from 2001 to 2007. The concentrations of organic contaminants in sediments along the Korean coast were relatively low or moderate compared with foreign studies. The mean detection frequencies of organic contaminants during the seven years were highest for PAHs and PCDD/Fs, followed by PCBs, DDTs, TBT and HCHs in decreasing order. Based on published sediment quality guidelines, the ecological risks of persistent organic pollutants in sediments along the Korean coast were low, despite exceedances of the ERL at 2-6 sites for DDTs, and the TEL at 9-18 sites for PCDD/Fs. Nonparametric tests to assess temporal trends revealed significant decreasing trends for PCBs and PCDD/Fs at four and three sites, respectively (p < 0.05). These results reflect the effects of regulations on the use of those contaminants.     

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.     

TEMPORAL AND SPATIAL DISTRIBUTIONS OF PAHS AND PCBS IN LAKE CALUMET AREA, CHICAGO

1 INTRODUCTION Lake Calumet is located 15 miles southeast of downtown Chicago. The geographical boundaries include 130th Street to the south, Stony Island Avenue to the east, an industrial area to the north, and interstate highway I-94 to the west. The major continuous water inflow to the lake is Pullman Creek, a drainage ditch, which carries the runoff from the nearby expressway, industries, and landfills into the lake at the northwest corner. The outlet of the Lake is the Calumet R…     

Tributyltin along the coasts of Corsica (Western Mediterranean): a persistent problem.

Despite optimistic forecasts by various scientists after regulatory measures were taken in the 1980s, coastal tributyltin (TBT) contamination is still a major problem. The present study concerning Corsica (Western Mediterranean) shows that contamination is not limited to harbour areas, but extends along the coast, involving protected nature reserves. The concentrations measured in harbours, which can reach 200 ng TBT l(-1), tend to incriminate both pleasure craft and ferries providing regular service between the island and the continent. Contamination as high as 7 ng TBT l(-1) has been measured in waters of the Scandola nature reserve, which is quite excessive given the no effect concentrations (NOEC) for marine fauna are around 1-2 ng TBT l(-1). The inadequacy of current regulations and their application are a major factor in this situation.     

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.     

The nationwide investigation of endocrine disruptors in sediment of harbours

Various types of endocrine disruptors or environmental hormones flow from their sources down into harbours through rivers and other watercourses, and are accumulated in sediment on the sea bottom. Tributyltin, which has been used as paint for ship bottoms, is considered one of the endocrine disruptors.In close cooperation with the other ministries and agencies, the Ports and Harbours Bureau of the Ministry of Land, Infrastructure and Transport carried out an investigation in 1999 to determine the actual condition of 12 endocrine disruptors in the sediment of 39 harbours, in order to gather fundamental data to be used in future examinations of policy. Furthermore, in 2000 the bureau chose seven harbours out of the above 39 harbours as subjects of an additional investigation regarding the surface distribution of endocrine disruptors in the harbour areas and the synchronistic change of accumulation of dioxin and other substances. As the result of the investigation regarding the surface distribution of endocrine disruptors accumulated in seven harbours, relatively high concentrations were measured in the innermost parts of harbours and the mouths of rivers. Synchronistic changes in the amount of dioxin and other substances accumulated in sediments of five harbours were determined. Small amounts of dioxin and other substances, including an especially small amount of coplanar-PCBs, were found in the layers formed before or around 1950. Relatively large amounts of these substances were measured in the upper layers formed during roughly 1960-1990, though no significant yearly differences in concentration could be identified. This result coincides with the facts that, during roughly 1960-1980, PCP and CNP were used as agricultural chemicals and full-scale production of PCBs started in 1960.     

Organotin levels in Nazaré canyon (west Iberian Margin, NE Atlantic) and adjacent coastal area

Organotin compounds (OTs) are ubiquitous in the marine environment and high concentrations (μg g(-1) range) in sediments from different coastal areas around the world have been reported. However, few reports have described the OTs contamination status in the offshore and deep sea environment. This work investigated organotin levels in Nazaré canyon for the first time. Levels of monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), diphenyltin (DPT), triphenyltin (TPT), dioctyltin (DOT) and trioctyltin (TOT) were quantified in sediment samples from the upper flanks of the canyon and from the adjacent coastal area. TBT levels detected in the canyon flanks are about two to three orders of magnitude lower than those found in the coastal area. Nevertheless, when quantifiable, TBT levels in the canyon samples were higher than the Environmental Assessment Criteria set for TBT in sediments by the OSPAR Commission indicating that at those locations negative ecological impacts are likely to occur.     

Baseline of butyltin pollution in coastal sediments within the Basque Country (northern Spain), in 2007-2008

Tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) were measured in surficial sediments at, the ports of Pasaia and Bilbao, together with other mid- and small-size harbours of the Basque Country (northern Spain), in 2007-2008. The highest values of the sum of the three measured butyltin species (3523-3640 ng g⁻¹, as Sn) were found at sampling stations near to shipyards located within the port of Pasaia. The highest value of TBT concentration (3143 ng g⁻¹, as Sn) was found at the marina of Getxo, in the port of Bilbao. The degree of TBT degradation varied greatly between sampling stations, being found to be generally higher in those sediments with higher values of redox potential and lower values of TBT concentration (normalized by organic matter content).     

Nutrient,heavy metal and organic pollutant composition of suspended and bed sediments in the Rhone River

The environmental quality of the Rhone River (Switzerland-France) has been assessed with a geochemical survey of the pollutants bound to suspended sediments. Ten samples were collected between Lake Geneva and the Mediterranean Sea in Nobember 1989 by continuous flow centrifugation and analysed for grain size distribution, carbonate, organic C, N, forms of particulate P, trace metals, and organic compounds (chlorobenzenes, organochlorine pesticides, PCBs, and PAHs). Four bed sediment samples were also studied for comparative purposes. The suspended solids provide lower variance by parameter than the bed sediments and are clearly most suitable for synoptic monitoring.The Upper Rhone River carries a glacial derived sediment with a low nutrient content, the stretch from Geneva to Lyon provides a sediment dominated by carbonate, and in the Lower Rhone the organic matter and phosphorus are relatively increased, mainly due to wastewater effluents and to an industrial P source. High concentrations of metals and organic micropollutants downstream of Lyon indicate a multiple contamination in the Lower Rhone, whereas more specific inputs are located downstream of Geneva and Arles.The comparison with data from other polluted major systems, the Rhine, the Niagara and the Detroit rivers, shows on overall similarity confirming that the Rhone quality is degraded downstream of Lyon. The levels of particular concern are for Hg, DDT metabolites which reveal a recent release in the basin, PCBs with a likely high chlorine content, and PAHs.The statistical evaluation of the compositional variables indicates a limited number of well defined associations, suggesting that the contamination of the suspended sediments results from the combination of numerous and intermittent point and diffuse sources in the Rhone River basin.