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Organotins in Swiss lakes after their ban: Assessment of water, sediment, and Dreissena polymorpha contamination over a four-year period
Abstract
The effect of a legal ban on antifouling paints containing organotin compounds (1988, to be fully enforced within two years) was studied in Swiss freshwater ecosystems. Between 1990 and 1993, organotins were monitored in water, sediment, and zebra mussel tissue (Dreissena polymorph) from four lakes (one marina and one natural reference site per lake). The analytical technique was a gas chromatography method using FPD detection after methylation or hexylation.
In the studied marinas, no significant decrease in concentrations was detected in sediment and zebra mussel tissue; a reduction was measured in water. The levels observed are probably due to the continuing use of antifouling paints still containing organotins, and to a slow degradation in sediment. A survey conducted among boat owners of the studied marinas allowed us to estimate that an average 25% of boats were still protected by organotin-containing antifoulings one to two years after the new legislation. Zebra mussels, used as biomonitors, showed very high concentrations of tributyltin (up to 49 μg/g dry weight). No shell thickening or other growth effect was observed. In the reference sites, much lower levels were detected.
... Tributyltin contamination of freshwater environmental media has been documented for a number of lakes and rivers exposed to recreational boating and commercial shipping activity (Chau 1986;Waite et al. 1989;Stang and Goldberg 1989;Becker van Slooten and Tarradellas 1995;Fent and Hunn 1995). The distribution of TBT contamination has been shown to be positively related to the degree of exposure to boating activity across a range of spatial scales, from individual river systems to wider regional zones Gomez-Ariza et al. 1998). ...
This study sought to determine whether tributyltin (TBT), a toxic environmental contaminant now banned from use in antifoulant paints, could have contributed to ecological degradation in shallow lakes. Anthropogenic stresses have often led to changes in ecological structure and functioning within such waterbodies, with catastrophic loss of submerged macrophytes a common phenomenon. An area that has experienced intense TBT contamination and widespread macrophyte loss, is the Broads, a popular inland navigable waterway in E. England. Development of an online SPE-LC-MSn analytical method enabled identification and quantification of contemporary organic antifoul biocides in water and sediment samples. This contemporary analysis improved understanding of the transport mechanisms that would have been responsible for dilution and dispersion of TBT. Within the River Bure study area, a distinct antifoul biocide contamination gradient was observed, that related to the level and type of boating activity. Most significantly, biocide transportation has led to areas not directly exposed to boating activity, but in hydrological connection, to become contaminated. The recent ecological histories of contaminated lakes was reconstucted using multi-proxy palaeoecological analytical techniques on cores collected using a new wide-diameter corer. Data from the radiometrically-dated cores indicated that at least twenty years of continuous TBT pollution occurred in the Broads, against a backgound of eutrophication. The pre-TBT period was characterised by presence of macrophyte remains with abundant plant-associated diatoms, cladocera and invertebrates, which switched to predominantly planktonic assemblages after initial detection of TBT. Environmental concentrations of TBT present during its active usage in antifoulant paints, would have adversely affected functionally important aquatic organisms, as indicated by ecotoxicological test data. The spatio-temporal assessment of contamination, combined with a palaeoecological approach, has been successful in reconstructing relative toxicant exposure and patterns of ecological change in the Broads. This methodology could be applied to the study of other persistent pollutants.
... Due to this fact, molluscs and especially freshwater and marine bivalves have widely been used as bioaccumulation indicators of TBT contamination in the past. Examples for such approaches are the investigations of Becker et al. (1992) and Becker-van Slooten and Tarradellas (1995) in Swiss lakes, using the zebra mussel Dreissena polymorpha, and the analyses of Short and Sharp (1989), Higashiyama et al. (1991), Page (1995), Phelps and Page (1997), Morcillo et al. (1999), Jacobsen and Asmund (2000) with different marine bivalves. ...
... – for charismatic mega-fauna see Blane and Jaakson 1994; Au and Green 2000; Laist et al. 2001; Nowacek et al. 2001; Erbe 2002; Jelinski et al. 2002; Williams et al. 2002; Lusseau 2003a; 2003b; Constantine et al. 2004; Lemon et al. 2006; Williams and Ashe 2007; Stamation et al. 2010; Work et al. 2010; Lachmuth et al. 2011; Tseng et al. 2011; Wiley et al. 2011; and Steckenreuter et al. 2012; – for antifoulants see Talbot 1986; Nichols 1988; Becker-van Slooten and Tarradellas 1995; de Mora et al. 1995; Matthiessen et al. 1995; Dahl and Blanck 1996; Michel and Averty 1999; Voulvoulis et al. 1999; Axiak et al. 2000; Albanis et al. 2002; Haynes and Loong 2002; Schiff et al. 2004; Sayer et al. 2006; Sapozhnikova et al. 2007; Srinivasan and Swain 2007; Carson et al. 2009; Singh and Turner 2009b; 2009a; Turner 2010; and Yu et al. 2011; and – for oil spills see LaBelle and Anderson 1996; Eberhardt and Garrott 1997; Ketkar and Babu 1997; Batten et al. 1998; Dean et al. 1998; Feder and Blanchard 1998; Lancaster et al. 1998; Glegg et al. 1999; Hughes 1999; Seiser et al. 2000; Garshelis and Johnson 2001; Born et al. 2003; Janiot et al. 2003; Nikitik and Robinson 2003; Andersen et al. 2008; Piñeira et al. 2008; Melville et al. 2009; Dalton and Jin 2010; Song et al. 2011; and Vidal et al. 2011Althaus et al. (2007) outline a range of policy options that are available to governments to achieve their objectives (environmental or otherwise). These include advocacy (such as campaigns to encourage desired behaviour), money (such as taxes and grants), government action (such as the provision of public services), and law (such as legislation and regulations). ...
PhD Thesis 2011. Griffith School of Environment, Science, Environment, Engineering and Technology, Griffith University, Gold Coast, Queensland, Australia.
Abstract
There are approximately 1,500 tour boat operators with a combined fleet of approximately 3,800 vessels offering various sailing, fishing and diving activities in Australia’s marine environments. Many of these operate within marine protected areas (MPAs), such as the Great Barrier Reef Marine Park (GBRMP), and have the potential to adversely impact on human health and the environment from the operation of their vessels. These boating related environmental impacts stem from emissions and/or discharges of sewage, garbage, oil, greenhouse gases, antifouling agents and the physical disturbance of substrates, flora and fauna from anchoring, grounding, engine/propeller noise, vessel movement, etc.. There are, however, various measures available to promote more sustainable management of these boating related environmental impacts that involve regulation, voluntary programs and economic prompts. This thesis investigates the specific boating related environmental impacts of the industry on the marine environment and identifies opportunities to improve the environmental performance of Australian tour boat operators with respect to the operation of their vessels. Fieldwork was undertaken in Cairns, the Whitsundays, the Moreton Bay/Gold Coast region, Sydney, Melbourne, Broome and Exmouth. This thesis provides the first account of the standards and practices of the Australian tour boat industry making an original contribution to this field through the collection, presentation and interpretation of the new data. It also identified that the most effective ways to promote this is through the better education of operators to promote behavioural changes and practical measures on board. It is argued that a national tour boat operator organisation could assist in reducing environmental impacts and making the industry more sustainable.
... A szabályozások következtében a TBT vízben mért koncentrációja csökkenésnek indult, de toxikus hatása az arra érzékeny vízi élőlényekre megmaradt. Ez utóbbi annak tulajdonítható, hogy a tiltások után is magas volt a TBT koncentráció a vizsgált üledékekben és vízi puhatestűekben[Becker-van Slooten et al. 1995]. Ezért 1990-ben az International Maritime Organization (IMO) javasolta a TBT tartalmú algagátló festékek használatának betiltását az egész világon. ...
Identification of ecosystem services, i.e. the contributions that ecosystems make to human well-being, has proven instrumental in galvanising public and political support for safeguarding biodiversity and its benefits to people. Here we synthe-sise the global evidence on ecosystem services provided and disrupted by freshwater bivalves, a heterogenous group of >1200 species, including some of the most threatened (in Unionida) and invasive (e.g. Dreissena polymorpha) taxa globally. Our systematic literature review resulted in a data set of 904 records from 69 countries relating to 24 classes of provision-ing (N = 189), cultural (N = 491) and regulating (N = 224) services following the Common International Classification of Ecosystem Services (CICES). Prominent ecosystem services included (i) the provisioning of food, materials and medicinal products, (ii) knowledge acquisition (e.g. on water quality, past environments and historical societies), ornamental and other cultural contributions, and (iii) the filtration, sequestration, storage and/or transformation of biological and physico-chemical water properties. About 9% of records provided evidence for the disruption rather than provision of ecosystem services. Synergies and trade-offs of ecosystem services were observed. For instance, water filtration by freshwater bivalves can be beneficial for the cultural service 'biomonitoring', while negatively or positively affecting food consumption or human recreation. Our evidence base spanned a total of 91 genera and 191 species, dominated by Unionida (55% of records, 76% of species), Veneroida (21 and 9%, respectively; mainly Corbicula spp.) and Myoida (20 and 4%, respectively; mainly Dreissena spp.). About one third of records, predominantly from Europe and the Amer-icas, related to species that were non-native to the country of study. The majority of records originated from Asia (35%), with available evidence for 23 CICES classes, as well as Europe (29%) and North America (23%), where research was largely focused on 'biomonitoring'. Whilst the earliest record (from 1949) originated from North America, since 2000, annual output of records has increased rapidly in Asia and Europe. Future research should focus on filling gaps in knowledge in lesser-studied regions, including Africa and South America, and should look to provide a quantitative valuation of the socioeconomic costs and benefits of ecosystem services shaped by freshwater bivalves.
The present paper aims at reviewing general knowledge of large European perialpine lakes as provided by sediment studies, and at outlining the contribution, from several lines of evidence, of modern paleolimnology in both interpreting past lake ecological evolution and forecasting lake responses to future human impacts. A literature survey mainly based on papers published in international journals indexed on ISI-Wos and Scopus from 1975 to April 2017 has been conducted on the 20 perialpine lakes with zmax ≥ 100 m and lake area ≥ 10 km², and on 4 shallower perialpine lakes representing hotspots of extensive neo- and paleo-limnological research. By pinpointing temporal and spatial differences in paleolimnological studies conducted in the Alpine countries, the review identifies knowledge gaps in the perialpine area, and shows how sediment-based reconstructions represent a powerful tool, in mutual support with limnological surveys, to help predicting future scenarios through the “past-forward” principle, which consists in reconstructing past lake responses to conditions comparable to those to come. The most recent methodological developments of sediment studies show the potential to cope with the increasing ecosystem variability induced by climate change, and to produce innovative and crucial information for tuning future management and sustainable use of Alpine waters.
Organotin compounds (OTC), particularly tributyltin, have been widely used since the mid-60s as biocides in antifouling paints, being considered as one of the most toxic xenobiotics ever produced and introduced into the environment. Because of their widespread use in numerous applications (industrial, agricultural, etc.) and their specific chemical and physical characteristics, these pollutants were detected in all aquatic ecosystems, with highest concentrations in the marine coastal and lagoon environments.
OTC are extremely toxic to a wide range of organisms, from bacteria to mammals, including humans; one of the most remarkable effects is “imposex”- the superimposition of male characters onto females of gonochorist gastropods.
This booklet is the result of 10-years activity on the study of OTC by the Scientific Technical Structure (STS) ISPRA of Chioggia. It provides information on the origin, chemistry, distribution, the effects of OTC, legislative regulations and the limits for these compounds on both national and international levels. More technical contents concern the sampling, preparation and storage of samples, as well as the methods of analysis in different environmental matrices such as water, sediment and biota. Evaluation methods of OTC effects on mollusks are also detailed. Finally, two technical sheets are included: the first shows the analytical method for the analysis of the OTC used in the laboratories of the STS ISPRA of Chioggia; the second one shows in detail the assessment method for the determination of imposex in gastropod mollusks.
This study evaluates the suitability of using Hyalella azteca as a predictor of the risk that tributyltin (MT) poses to freshwater invertebrates by comparing the toxicity and bioaccumulation of TBT in H. azteca to five species: Hexagenia limbata, Physella gyrina, Tubifex tubifex, Chironomus riparius and Daphnia magna. Young from each species were added to aquaria containing sediment spiked with TBT concentrations of 0, 28.6,258 and 1900 ng Sn/g dry weight. Chironomus riparius data could not be quantified reliably due to poor control survival. Bioaccumulation of TBT in the five remaining species was similar at sediment concentrations of 258 ng Sn/g, and the bioaccumulation relationships of P. gyrina and H. azteca were virtually identical. No toxicity was evident in any test species at body concentrations of 1100 to 1800 ng Sn/g. Body concentrations of 4000 to 6000 ng Sn/g were associated with significant (p < 0.05) mortality in H. limbata, P. gyrina, T. tubifex and D. magna, but not in H. azteca. However, bioaccumulation of TBT in H. azteca was comparable and can be used in predicting the effects of environmental TBT concentrations on these four species of freshwater invertebrates.
A survey of five marinas and one reference site on Lake Ontario, Canada, was conducted to investigate the occurrence and variation of tributyltin (TBT) levels in water between April and December of 1998. The survey results revealed the presence as well as seasonal trends of TBT in these marinas. The TBT concentrations in water were found to coincide with boating activity. The level of TBT generally rose in summer when the boating activity was high, and the highest level of TBT found was 14 ng Sn/L. On average, 92% of the TBT was in the operationally defined 'dissolved phase' in the waters analyzed. The butyltin compounds were also found in surface sediment and paint chips from some non-aluminum hulled pleasure boats, with total concentrations of butyltin species (including dibutyltin and monobutyltin) ranging from 59 to 570 ng Sn/g dry weight, and from 0 to 146 μg Sn/g, respectively. The results clearly indicated that TBT in the marina waters primarily originated from antifouling paint on pleasure boats, even though the use of TBT as an antifouling agent was regulated in 1989.
The extremely toxic antifouling pesticide tributyltin (TBT) was regulated in many countries in the 1980s and 1990s. The regulations have been successful in reducing the toxic threat posed by TBT in many locations around the world. However, there are also many locations at which recovery has not been seen, even 10 years after regulation. Because of continuing concern about the environmental hazards of TBT, the International Maritime Organization proposes to prohibit all antifouling uses of TBT by 2003, and the presence of TBT on ship hulls by 2008. Canada has recently announced a prohibition on the use of organotin antifouling paints by January 1, 2003. This article reviews the persistence, bioaccumulation and toxicity of TBT in aquatic environments, and concludes that TBT meets all such criteria for designation as a Track 1 substance under Canada's Toxic Substances Management Policy, necessitating measures to virtually eliminate it from the Canadian environment. Because of the long persistence of TBT in sediment, there may be a 'legacy problem' in sediments in some locations in Canada for perhaps 20 to 30 years after a total ban.
This study was designed to: (1) evaluate dibutyltin (DBT) and tributyltin (TBT) bi-weekly in the water column for four months during the peak boating season (June–September, 1989) at seven stations in the Back Creek and Severn River area of Maryland waters of Chesapeake Bay; (2) compare butyltin values from the 1989 study with values obtained from a similar butyltin monitoring study conducted in 1988 (after Maryland TBT legislation) and 1986 (before Maryland TBT legislation); (3) determine the extent of TBT paint use in the Back Creek area by surveying boat owners; (4) determine dissolved copper concentrations from three of the seven stations bi-weekly during the four-month study; and (5) compare dissolved copper concentrations at these stations with previous copper data collected in 1988.
Mean four-month DBT concentrations ranged from 10 to 73 ng/L at the seven stations. Highest DBT concentrations occurred at Station 1 in a marina; lowest concentrations occurred at Station 7 in the Severn River. Mean four-month TBT concentrations ranged from 177 ng/L at Station 1 (marina) to 21 ng/L at Station 7 (Severn River). Maximum TBT concentrations of 361 and 570 ng/L occurred at marina SDtations 1 and 3, respectively. Temporal trends in both DBT and TBT (station mean concentrations by date) showed that peak concentrations occurred during the early part of the boating season followed by reductions in late summer and early fall. Spike concentrations of both DBT (117 and 62 ng/L) and TBT (308 and 366 ng/L) were reported on two sampling dates near a boat maintenance facility in Back Creek.
There was a significant reduction in DBT concentrations from 1986 to 1989 when date was treated as a fixed effect. However, TBT concentrations were not significantly reduced between 1986 and 1989 when mean concentrations of TBT were averaged across stations and dates for each year. A significant reduction was reported at Station 1 (marina station) when each station was examined for differences between years. TBT was also reported to significantly decrease (p=0.0442) at Station 7 between 1988 and 1989. A boat owner survey in the study area showed that 6% of the recreational boats that were surveyed were painted with TBT paint in 1989. This was a significant decrease in TBT paint use from the previous year when 31% of recreational boat owners surveyed used TBT paints.
An evaluation of dissolved copper concentrations at three stations in the study area in 1989 showed that mean concentrations from bi-weekly sampling for four months was 10 μg/L at Station 1, 7.8 μg/L at Station 4 and 2.7 μg/L at Station 7. Copper concentrations decreased with distance away from the Back Creek marinas. Copper concentrations at all three stations were significantly lower in 1989 than in 1988.
A comprehensive method for trace analysis of mono-, di-, tri-, and some tetrasubstituted organotin compounds is presented. The ionic compounds are extracted from diluted aqueous solutions as chlorides by using a Tropolon-C/sub 18/ silica cartridge and from sediment and sewage sludge by using an ethereal tropolon solution. The extracted organotin compounds are ethylated by a Grignard reagent and analyzed by using high-resolution gas chromatography with flame photometric detection (HRGC/FPD). Gas chromatography/mass spectrometry (GC/MS) was used for confirmation. The extraction behavior, gas chromatographic retention, and photometric response of a series of organotin compounds are described, and the identification via electron impact (EI) and chemical ionization (CI) mass spectrometry is discussed. The main organotin compounds detected in various samples are butyltins; cyclohexyl- and phenyltins were identified in some of the sediment and sewage sludge samples. Methylbutyltins and tetrabutyltin were not detected. Concentrations were found to range from low ng/L (part per trillion) in surface water to low mg/kg (parts per million) in sewage sludge.
Populations of dogwhelks Nucella lapillus in areas of high boating activity on the Northumbrian coast had severe symptoms of imposex when they were sampled in 1986. They had high RPSI scores, male-biased sex ratios (probably due to high female mortality) and poor reproductive performance. There has however been marked recovery of these populations since the partial ban on the use of anti-fouling paints containing triorganotin compounds in 1987. RPSI values are lower, recruitment has improved and there is evidence of better survivorship of females.
1. Low level TBTO (bis(tributyltin)oxide) treatments (0.2 μg/l) caused, in vivo, a secretion of a calcified organic matrix over the inner face of the shell of Anodonta cygnea after eight days.2. Electrophysiological studies carried out on the outer mantle epithelium (OME) showed that the short-circuit current was strongly inhibited by TBTO from the shell side. On the contrary, the effect is very slow from the haemolymph side.3. The TBTO effect on the proton and/or bicarbonate transport mechanisms across the OME can be a strong factor in the shell thickening.
Juvenile Crassostrea gigas stock were experimentally deployed in 1989 at three locations within Poole Harbour (Dorset, UK); a mariculture and boating centre characterized until 1987 by high TBT levels, and abnormal shell thickening in C. gigas, preventing culture. After six months, the stock grown at sites adjacent to shellfish beds and featuring low boat densities, showed normal growth, whereas that grown within an embayment featuring high boat densities, showed the onset of abnormal thickening. Grossly thickened senescent C. gigas recovered from a commercial shellfish bed showed recent reversion to normal growth. These results suggest that since the 1987 UK restrictions on TBT use, levels within much of the Harbour have declined sufficiently to allow a return to C. gigas mariculture, but that levels remain too high within areas of high boat density.The study also compares the effectiveness of three established methods for assessing the degree of shell thickening.
A series of phenyltins and butyltins were determined in the water column, sediment, and biota of two freshwater marinas of Lake Lucerne, Switzerland. Considerable concentrations of triphenyltin (TPT), diphenyltin (DPT), and monophenyltin (MPT) were found for the first time in all the compartments. In addition, tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) occurred in significant concentrations. During 1988-1990, aqueous TBT concentrations followed a seasonal pattern with increases of up to 752 ng/L in late spring, followed by a successive decrease until winter, when concentrations remainded around 100 ng/L. TPT and TBT concentrations decreased during the observation period. Of the total aqueous TBT, 95-99% was present in the dissolved phase. In mussels Dreissena, TPT and TBT residues ranged up to 3.88 and 9.35-mu-g/g, respectively. Vertical sediment core profiles showed highest TPT and TBT concentrations of up to 107 and 2043-mu-g/kg, respectively, in the top with decreasing values with depth. Dating of the core and the occurrence of only low concentrations of DBT and MBT indicate that TBT is conserved in these sediments over a time period of years.