Butyltin Concentrations Research Articles

Assessment of imposex and butyltin concentrations in Gemophos viverratus (Kiener, 1834), from São Vicente, Republic of Cabo Verde (Africa).

This work constitutes the first assessment of tributyltin (TBT) pollution levels in the Republic of Cabo Verde (Africa) and proposes the marine gastropod Gemophos viverratus (Kiener, 1834) as a new bioindicator of TBT pollution in the Macaronesia and west coast of Africa. Specimens were collected between August and October 2012 along a gradient of naval traffic in São Vicente Island. The results clearly indicate an increase of imposex levels (percentage of females affected with imposex, 0-100 %; vas deferens sequence index, 0-4.1; relative penis length index, 0-54.6 %) and female TBT contamination (from 5 to 37 ngSn g(-1) dry weight (dw)) from outside to inside the harbour of Porto Grande Bay and identify this area as the focus of TBT pollution in the island. The butyltin degradation index for G. viverratus tissues ranged between 1.3 and 2.2, which being above 1 suggests that a considerable part of TBT inputs to the bay may not be very recent. Sterile females were found inside the harbour with an incidence up to 21.4 %. Considering the existence of a planktonic veliger stage in the life cycle of G. viverratus, it is expected that recruitment of newborn individuals can be supplied from unaffected breeding females inside and outside the Porto Grande Bay, resulting in a reduced impact of TBT pollution on population abundance. G. viverratus is very promising to be used as a simple, inexpensive and efficient novel tool for TBT pollution biomonitoring in the Macaronesia and west coast of Africa, a region for which there is an astonishing lack of information concerning levels and ecological impacts of TBT pollution.

Differential organotin sensitivity in two Leucozonia species from a ship traffic area in southeastern Brazil

Tributyltin exposure is the primary cause of imposex development in gastropods, making them excellent bioindicators. The present research represents the first examination of butyltin (BT) contamination in surface sediments associated with imposex in Leucozonia nassa and L. ocellata in a harbour complex area in Espírito Santo, southeastern Brazil. The objectives of this study were to evaluate the organotin pollution in the area and to assess the sensitivity of both species to BT pollution through imposex development. Specimens were collected between 2007 and 2010 and the sediments were sampled in 2007. Imposex intensity was evaluated based on the percentage of imposexed females, the relative penis length index (RPLI) and the average value of the vas deferens sequence index (VDSI). BTs were analysed using gas chromatography equipped with a pulsed flame photometric detector (PFPD). The results demonstrated the occurrence of elevated concentrations of BTs in the sediment ranging from 383.7 to 7172.9 ng Sn g−1, indicating a severe contamination of the area, which was confirmed by the biological monitoring results. Our findings also indicated that L. ocellata is a less sensitive species than L. nassa and that this differential sensitivity plays a key role in the distributions of the populations of both species in the studied area.

Risk assessment of butyltins based on a fugacity-based food web bioaccumulation model in the Jincheng Bay mariculture area: II. Risk assessment.

A fugacity-based food web bioaccumulation model was constructed, and the biotic concentrations of butyltins in the food web of the Jincheng Bay mariculture area were estimated accordingly, using the water and sediment concentrations described in the accompanying paper (Part I). This paper presents an ecological risk assessment (ERA) and a human health risk assessment (HHRA) of the butyltins, based on the estimated tissue residues in the marine life in this area. The results showed that the ecological risk probability was greater than 0.05. At this level, management control is critical since sensitive marine species would be profoundly endangered by butyltin contamination. Few if any detrimental effects, however, would be generated for humans from exposure to butyltins through seafood consumption. The fugacity-based model can refine the ERA and HHRA of pollutants in marine areas, provide a basis for protecting marine ecology and the security of fishery products, and thus help determine the feasibility of a proposed aquaculture project.

Organotin pollution from pleasure craft at Paraty, a tourist area of Southeastern Brazil: amelioration or interference?

Some organotin compounds, such as TBT, are endocrine disruptors and harm marine ecosystems. Even after the global ban on organotins, increasing imposex levels have been detected in Stramonita haemastoma analyzed in 2004 and 2011 in some locations at Paraty, a tourist area in southeastern Brazil. The results of this study indicate that particulate and dissolved organic carbon and xenoestrogens might be interfering in this syndrome's development, leading to underestimation of imposex evaluation. Chemical analysis of three mangrove swamp sediments in the area showed the presence of TBT (16.0 - 205.7 ng Sn g-1), DBT (10.1 - 16.4 ng Sn g-1) and MBT (10.1 - 10.2 ng Sn g-1) even at the reference sites. The concentrations of butyltins and the increased incidence of imposexat some stations indicate recent inputs of TBT in the study area due to its illegal use on small vessels.

Trace elements in the sediments of a large Mediterranean marina (Port Camargue, France): Levels and contamination history

The study of trace elements (Cu, Zn, Pb, As, Hg) and butyltin concentrations in the sediments of Port Camargue enabled assessment of the levels and history of the contamination of the largest European marina linked with the use of antifouling paints. Surface sediments near the boat maintenance area were heavily contaminated with up to 1497μgg−1 of Cu, 475μgg−1 of Zn, 0.82μgg−1 of Hg, 94μgg−1 of Pb and over 10,000ngSng−1 of tributyltin (TBT). High concentrations of Hg and TBT indicate ongoing sources of these elements despite the ban on their use as biocides in paints. Sediment cores provided records of contamination since 1969. The peak concentrations of As, Hg, Pb and TBT in the sediment profile reflect their presence on boat hulls when the marina was built at the end of the 1960s. Degradation of TBT in the sediments near the boat maintenance area is slow compared to other less contaminated area of the marina.

Imposex and butyltin burden in Bolinus brandaris (Mollusca, Gastropoda) and sediment from the Tunisian coast

The present study aimed at analyzing the imposex incidence and the presence of butyltins namely tributyltin (TBT) with its di- and mono-substituted metabolites in Bolinus brandaris whole tissues and in surface sediments at seven sites from the Tunisian coast during one campaign in May 2010. Butyltin levels were evaluated using isotope dilution GC–MS. Except the population collected from Zarat site, imposex was found in snails from the remained six sites with a maximal incidence and sterility (closure of the vaginal opening) registered in Carrier bay. Both imposex indices VDSI and RPLI showed a positive correlation with tissue concentrations of TBT. Total butyltin concentrations in sediments were higher in sites located in the vicinity of shipping areas with levels of TBT high enough to cause environmental concern if there is no legislative restriction and enforcement for the sale and use of these chemicals in Tunisia. These results further confirmed that B. brandaris is a good bioindicator of butyltin pollution in the studied areas. In addition, this study provided recent and new data on sediment butyltin concentrations that could serve for long-term monitoring of TBT pollution in Tunisia and the Mediterranean Sea.

Evidence of Butyltin Biomagnification along the Northern Adriatic Food-Web (Mediterranean Sea) Elucidated by Stable Isotope Ratios

The biomagnification of tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), and total butyltins (ΣBT) was analyzed in the Northern Adriatic food-web (Mediterranean) considering trophodynamic interactions among species and carbon sources in the food-web. Although it is acknowledged that these contaminants bioaccumulate in marine organisms, it is still controversial whether they biomagnify along food-webs. A wide range of species was considered, from plankton feeders to top predators, whose trophic level (TL) was assessed measuring the biological enrichment of nitrogen stable isotopes (δ(15)N). Carbon isotopic signature (δ(13)C) was used to trace carbon sources in the food-web (terrestrial vs marine). At least one butyltin species was detected in the majority of samples, and TBT was the predominant contaminant. A significant positive relationship was found between TL and butyltin concentrations, implying food-web biomagnification. Coherently, the Trophic Magnification Factor resulted higher than 1, ranging between 3.88 for ΣBT and 4.62 for DBT. A negative but not significant correlation was instead found between δ(13)C and butyltin concentrations, indicating a slight decreasing gradient of contaminants concentrations in species according to the coastal influence as carbon source in their diet. However, trophodynamic mechanisms are likely more important factors in determining butyltin distribution in the Northern Adriatic food-web.

Resistance to oxidative damage but not immunosuppression by organic tin compounds in natural populations of Daubenton's bats (Myotis daubentonii)

The acute toxicity of organic tin compounds (OTCs) has been studied in detail. However, due to their complex nature, very little is known about species-specific methods of accumulation and consequences for food-webs. Chironomids, on which e.g. Daubenton's bats feed, may act as vectors for the transport of organic tin compounds from aquatic to terrestrial ecosystems. Bats are prone to environmental toxins because of their longevity and their ecological role as top predators. Organic tin compounds are associated with increased formation of reactive oxygen species and associated oxidative damage as well as suppression of immune function. The present paper investigates whether the OTC, tributyltin (TBT) and its metabolite, dibutyltin (DBT), accumulate in natural populations of Daubenton's bats and whether TBT-associated effects are seen in general body condition, redox balance, redox enzyme activities, associated oxidative damage of red blood cells and complement function. We discovered the concentration of bat fur DBT correlated with local marine sediment TBT concentrations. However, we did not find a correlation between the explanatory factors, bat fur DBT and marine sediment TBT concentrations, and several physiological and physical response variables apart from complement activity. Higher DBT concentrations resulted in weaker complement activity and thus a weaker immune response. Although the observed physiological effects in the present study were not strongly correlated to butyltin concentrations in fur or sediment, the result is unique for natural populations so far and raises interesting questions for future ecotoxicological studies.

Organotin compounds in surface sediments from selected fishing ports along the Chinese coast

The concentrations and species of organotin compounds (OTCs) in 52 surface sediment samples from nine fishing ports along the Chinese coast were studied. Butyltins (BTs) and phenyltins (PhTs) were derivatized using sodium tetraethylborate (NaBEt4) and determined by head-space solid-phase microextraction (HS-SPME) gas chromatography coupled with a flame photometric detector (GC-FPD). The concentrations of OTCs ranged from <3.6 to 194 ng (Sn) g−1 dry weight (dw) for monobutyltin (MBT), <2.3 to 41.5 ng (Sn) g−1 dw for dibutyltin (DBT), <0.7 to 86.0 ng (Sn) g−1 dw for tributyltin (TBT) and <5.1 to 66.1 ng (Sn) g−1 dw for monophenyltin (MPhT), respectively. The concentrations of diphenyltin (DPhT) and triphenyltin (TPhT) were below the limit of detection (LOD). BTs were the main species in the sediments except for the samples collected from Shazikou fishing port in Qingdao. The concentrations of MBT were higher than DBT and TBT. The concentrations of OTCs in the sediments varied widely among different sampling locations. The concentrations of BTs were much higher in the samples collected from fishing ports close to the South China Sea than those in coast of the East China Sea and the Yellow Sea. MPhT was prevalent in most sampling stations except for those in coast of the East China Sea. The environmental and ecotoxicological risks of TBT in most sediment samples were low.

Butyltin compounds in liver of harbour porpoises (Phocoena phocoena) from the UK prior to and following the ban on the use of tributyltin in antifouling paints (1992–2005 & 2009)

Liver butyltin concentrations (monobutyl, dibutyl and tributyltin (TBT)) in harbour porpoises (n=410) have been determined during 1992–2005, and again in 2009 following a ban on the use of tributyltin-based antifouling paints on ships. The aim was to assess the effectiveness of the regulation, which was implemented during 2003–2008. Since the ban was put in place summed butyltin concentrations have declined. Also, the percentage of animals in which TBT was detected has fallen sharply, indicating the cessation of fresh inputs. In 1992, 1993 and 1995, TBT was detected in 100% of samples analysed. In 2003–2005, once the implementation of the ban had begun, this fell to 61–72%, and in 2009, following the completion of the ban, had reduced to 4.3% (i.e. in only 1 of 23 samples analysed). Thus we conclude that the ban has proved effective in reducing TBT inputs to the seas from vessels.

&amp;lt;i&amp;gt;Mytilus galloprovincialis&amp;lt;/i&amp;gt; as Mussel Watch for Butyltins, Tin, Copper and Zinc Contamination, from Antifouling Paint Particles, in West Algerian Coastal Waters

Butyltin compounds (BTs) including tributyltin (TBT) and its degradation product (DBT) and concentrations of heavy metals (Sn, Cu and Zn) were determined in mussels (Mytilus galloprovincialis) collected from some West Algerian harbours. BTs were detected in all the mussels. Quanti?cation of BTs and heavy metals was carried respectively by Gas Chromatography coupled with Mass Spectrometer (GC-MS) and Atomic Absorption Spectrometry, flame AAS. Concentrations of total butyltin (BTs: DBT + TBT) in mussels ranged from 0.49 to 2438 ng/g wet wt. The concentrations (μg/g wet wt) of heavy metals ranged from 0.40 to 3.55 for Sn, 9.62 to 67.03 for Cu, and 87.13 to 731.51 for Zn. Total of tin in mussels ranged from 0.2 to 1054.78 ng/g. Higher concentrations of butyltin compounds were found in mussels collected from Mers El Kebir shipyard, Arzew, a petroleum harbour (industrial), and Beni Saf fishing harbour. This suggested that maritime activities nearby the harbours play a major role as the source of BTs. Indeed, harbour of Arzew is frequented by voluminous tanker. TBT was the predominant compound in mussels collected from almost all the sampling locations; indicate the fresh input of TBT in harbours.

Shell disturbances and butyltins burden in commercial bivalves collected from the Bizerta lagoon (northern Tunisia)

Shell disturbances and soft tissues butyltin burden were investigated in commercial bivalves Lithophaga lithophaga, Mytilus galloprovincialis, Solen marginatus and Crassostrea gigas from the Bizerta lagoon. Shell disturbances were found in all bivalves, being scarce in S. marginatus. In the internal valve of L. lithophaga, burrowing annelids and sipunculids living inside galleries were observed, while in the external valve, brown-blackish or white stains were found. In M. galloprovincialis, a yellowish mass located at the shell anterior side was found fixed firmly to the pearly layer by a hard brownish structure covering some annelid elliptic eggs. In the internal shell layer of some specimens collected in April, embryos belonging to tubiculous annelids at various developmental stages were observed. In C. gigas, shell thickening was revealed in some specimens corresponding to white doughy deposits at the internal valve and between shell layers. In S. marginatus, only one specimen showing a cavity at the posterior site was found. Total butyltin concentrations in the studied bivalves varied between 30 and 245 ng/g dry weight with tributyltin (TBT) being the predominant compound. The highest concentration was recorded in L. lithophaga collected from the Bizerta Bay and the lowest concentration in S. marginatus from Maghraoua. This study provided baseline data that could serve for long-term monitoring of TBT pollution in Tunisia, since legislation to reduce the use of TBT-based antifouling paints has not been introduced yet.

Simultaneous determination of mercury and butyltin species using a multiple species-specific isotope dilution methodology on the European, Anguilla anguilla glass eel and yellow eel

A methodology to simultaneously determine mercury (MeHg, IHg) and butyltin (TBT, DBT, MBT) compounds in eel samples was assessed and validated using multiple isotopically enriched species. The developed methodology was able to analyse simultaneously the organometal species accurately and precisely and to correct for the potential transformations/degradations of the different species during the various steps of the analytical procedure. Low detection limits were achieved (0.007–0.17 µg Hg kg−1 for mercury (Hg) species and 0.42–0.71 µg Sn kg−1 for tin (Sn) species) allowing analysis of low-mass samples and thus the analysis at the individual organism scale, including glass eels for which samples dry weight ranged from 60 to 100 mg. The methodology was validated with certified reference materials (BCR-464, BCR-477, BCR-710, DOLT-4 and NIST-2977) and applied to the analysis of these pollutants in two developmental stages of the European eel, Anguilla anguilla: individual whole glass eels and muscle tissue from yellow eels. The Adour estuary (South-west France) was selected to monitor the bioaccumulation of organometal species in these organisms, according their developmental stage, their morphological parameters and the sampling site. The results suggest that the accumulation of methylmercury in glass eel tissue is related to weight, with higher concentrations in smaller individuals. Butyltin concentrations were very close to the limit of detection, and no significant differences were detected between glass and yellow eels.

Butyltin compounds in vinegar collected in Beijing: Species distribution and source investigation

Forty-eight vinegar samples including white vinegar, rice vinegar and mature vinegar were collected from several markets in Beijing. Butyltin compounds were determined by headspace solid-phase microextraction coupled with gas chromatography and flame photometric detector after in situ ethylation with sodium tetraethylborate. Butyltin species were detected in sixteen vinegar samples and ranged from 0.012 to 14.10 μg Sn L−1. The detection rate of white vinegar is higher than that of rice vinegar and mature vinegar. Vinegar samples with relatively high butyltin concentration (>1.5 μg Sn L−1) were those stored in plastic bags, indicating that the plastic bag was one of the possible sources of butyltin contamination. This was further confirmed by the leaching experiments of three selected plastic bags, and monobutyltin was detected in the leaching solvents. According to the estimation, the average daily intake of total butyltin compounds through vinegar consumption is about 0.04 ng Sn/kg b.w., much lower than the Tolerable Daily Intake (TDI) of 100 ng Sn/kg b.w. set by the European Food Safety Authority (EFSA).

Life history-related organotin body burden in the catadromous eels Anguilla marmorata and A. bicolor pacifica in Vietnam

In order to understand the ecological risks caused by organotin compounds (OTs) in diadromous fish migrating between sea and freshwater, tributyltin (TBT) and triphenyltin (TPT) com- pounds, and their breakdown products, were determined in the catadromous eels Anguilla mar- morata and A. bicolor pacifica, collected in Vietnam waters. Ontogenic changes in otolith strontium (Sr) and calcium (Ca) concentrations were examined along life history transects in order to determine habitat use in the eel. There were generally no significant correlations between TBT and TPT accu- mulation and various biological characteristics such as total length (TL) and body weight (BW). In A. bicolor pacifica, TBT and the total butyltin (BT) concentrations of yellow-stage eels (immature eels) were significantly higher than those in silver-stage eels (mature eels). This suggests that yellow-stage eels have a higher risk of contamination by TBT than silver-stage individuals. Positive linear relation- ships were found between Sr:Ca ratios, total BTs and total phenyltins. These results suggest that the ecological risk of OTs in these eels increases with increasing sea residence period. Thus, migratory history and maturation stage are the most important factor for OT accumulation in catadromous eels.

Enzymatic activities in spermatozoa and butyltin concentrations in Baltic turbot ( Scophthalmus maximus)

Spermatozoal enzymes of fish (NAD +- and NADP-dependent dehydrogenases and creatine kinase (CK)) were previously determined to be sensitive to tributyltin (TBT) in laboratory experiments and were thus indicated for use as biomarkers for TBT exposure. However, the potential ability of spermatozoal enzymes as biomarkers of TBT exposure has never been recapitulated in a field study. For this purpose, the kinetic activities of spermatozoal enzymes of the natural turbot Scophthalmus maximus population from the Gulf of Gdańsk (GDA) and the Pomeranian Bay (POM) in the southern Baltic Sea were measured. Gas chromatography/high-resolution mass spectrometry was used to determine the concentrations of TBT and its breakdown products, dibutyltin (DBT) and monobutyltin (MBT), in the muscle, liver and testes of the male turbot. Males from GDA had significantly higher enzymatic activities and butyltin (BT) content in tissues than those from POM. A general linear model (GLM) showed that lactate dehydrogenase (LDH), malate dehydrogenase (MDH), glucose-6-phosphate dehydrogenase (G6PDH) and CK activities increased significantly with BT concentration in the testes and liver. We indicate the potential effects of TBT pollution on the spermatozoal enzymes of Baltic turbot.

Baseline of butyltin contamination in sediments of Sundarban mangrove wetland and adjacent coastal regions, India

The study reports the first assessment for the quantification and speciation of butyltins (BTs) in surface marine sediment samples (0-5 cm) from intertidal mudflats of Sundarban mangrove wetland along with the Hugli (Ganges) river basin, eastern coastal part of India. Concentrations of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) were monitored at 16 stations and present at all study areas, in concentrations in sediments up to 84.2, 26.4 and 48.0 ng g(-1) of TBT, DBT and MBT, respectively. Significant correlations were obtained between MBT and DBT (r = 0.62, p = 0.01) and DBT and TBT (r = 0.54, p = 0.03). Calculated BT degradation index (BDI) values indicated recent contamination of BTs at 8 stations, and suggested either no degradation of TBT or very recent degradation at a 4 further stations. Additionally, BDI values also indicated no recent inputs of BTs in 4 stations (only MBT present in one of these stations). High concentrations of BTs, particularly TBT, have the potential to induce ecotoxicological impacts based on levels specified in Australian Sediment Quality Guidelines (SQGs). This study indicated that the majority of the analyzed stations were in the highest range of priority, due to high TBT concentrations.

Accumulation of butyltin compounds in cetaceans from Korean coastal waters

Data on the occurrence and accumulation profiles of butyltins (BTs), including tributyltin (TBT), in marine mammals are scarce. This is the first study to investigate residue levels and accumulation patterns of BTs in cetaceans from Korean coastal waters. The total concentrations of BTs (sum of mono- to tri-butyltins) in minke whales (Balaenoptera acutorostrata) and long-beaked common dolphins (Delphinus capensis) ranged from 15.7 to 297ng/g wet weight (mean: 100ng/g wet weight) and from 59.0 to 412ng/g wet weight (mean: 228ng/g wet weight), respectively. Dibutyltin (DBT) accounted for 63% of the total BTs in all cetacean samples. Significant species-specific differences in BT concentrations, possibly due to the differences in their habitat and diet, were found between the two cetacean species. The concentrations of DBT and TBT in most cetacean samples exceeded the threshold value for cytotoxic effects in cetaceans, implying potentially adverse health risks from exposure to BTs.

Seasonal variations of imposex indices and butyltin concentrations in the rock shell Thais clavigera collected from Hong Kong waters

This study investigated butyltin contamination in Hong Kong waters using the rock shell Thais clavigera as a biomonitor. We collected rock shells from nine coastal sites in both winter 2005 and summer 2006 to examine the spatial and seasonal patterns. The relative penis size index (RPSI) and vas deferens sequence index (VDSI) were determined following a standard protocol, while the tissue concentrations of butyltins (i.e., mono-, di- and tri-butyltin) were measured using gas chromatography. The results showed that imposex was particularly severe in T. clavigera collected from Victoria Harbour, Pak Sha Wan and Sai Kung Pier where shipping activities were frequent. Both imposex indices had a positive correlation with tissue concentration of tributyltin in T. clavigera. While VDSI exhibited little seasonal variation, RPSI of winter specimens was significantly higher than that of summer specimens. Thus, sampling season should be standardised when using RPSI as a biomarker.

Imposex and butyltin concentrations in snails from the lagoon of Bizerta (Northern Tunisia)

Imposex and butyltin concentrations were assessed in Hexaplex trunculus, Conus mediterraneus, Cyclope neritea and Nassarius mutabilis from Menzel Jemil, and H. trunculus and Stramonita haemastoma from the Bizerta channel. All females of the five species exhibited the characteristic development of male sex organs (penis and/or vas deferens). In Menzel Jemil, H. trunculus and C. mediterraneus exhibit similar imposex levels and were most affected (VDS reading 3–4). The development of a bud penis or a vas deferens sequence behind the right ocular tentacle was reported in Cyclope neritea and N. mutabilis (VDS 1). The concentration of tributyltin (TBT) was similar for the four species. The monobutyltin (MBT) was only detected in C. mediterraneus while the dibutyltin (DBT) was found in all gastropods at similar proportions as TBT. In the Bizerta channel, imposex levels were similar in both H. trunculus and S. haemastoma but imposex degree was higher in H. trunculus. This finding was confirmed by higher TBT concentration recorded in female of H. trunculus. These results suggested that H. trunculus is the more suitable bioindicator for monitoring TBT pollution.