Butyltin Compounds Research Articles

Evaluation of cloud point extraction coupled with fluorescence spectroscopy and multivariate curve resolution–alternating least squares for tributyltin determination in sediment samples

In this work, a new procedure for tributyltin (TBT) detection in marine sediments based on cloud point extraction (CPE) followed by total fluorescence spectroscopy combined with multivariate curve resolution–alternating least squares (MCR–ALS) is proposed. The multivariate model satisfactorily achieved the second order advantage in the presence of uncalibrated interferences, such as butyltin compounds or metallic species that are commonly found in sediment sample extracts. Under optimal conditions, the detection limit reached 3.0μg Sn L−1, and the relative prediction error was lower than 10%. The accuracy of the method was validated with the analysis of a certified sediment sample (marine sediment PACS-2), and there was good agreement between the certified and experimental results. Finally, the proposed methodology was satisfactorily applied to spiked real sediment samples, demonstrating the suitability of the proposed method for TBT detection in contaminated sediment samples.

Butyltin compounds in sediment and biota from the lagoon of Bizerte (northern Tunisia): Potential risk for consumers?

ABSTRACTLevels of butyltins (BTs) were monitored in sediment samples and in seven fish species (Boops boops, Diplodus sargus, Sarpa salpa, Serranus scriba, Spicara smaris, Trachurus draco, and Trachinus mediterraneus), five bivalve species (Cerastoderma glaucum, Chlamys flexuosa, Mytilus galloprovincialis, Pinna nobilis, and Ruditapes decussatus), two gastropod species (Bolinus brandaris and Hexaplex trunculus), cuttlefish (Sepia officinalis), and shrimp (Penaeus notialis), most of which are commonly consumed in Tunisia. Samples were collected from Bizerte lagoon during March 2012. Average concentrations of total BTs found in sediment and the muscle of fishes, bivalves, gastropods, cuttlefish, and shrimp were 17.7, 11.5, 31.8, 36.9, 8.1, and 9.4 ng Sn g−1 dw, respectively. The calculation of tolerable average residue levels and non-cancer hazard quotient for tributyltin (TBT) showed that daily exposure of these seafood to TBT is unlikely to cause any deleterious effects to humans, thus indicating that consumers may not be at risk through the inclusion of these species in their regular diet.

Use of Polydimethylsiloxane Preconcentration Sorbent for the Analysis of Organotins in Water Samples

Organotin compounds were extensively used as powerful biocides in anti-fouling paints and pesticide formulations, particularly tributyltin (TBT), and are recognized as priority pollutants by the european European Water Framework Directive (WFD). Environmental Quality Standard set by the WFD for TBT is fixed at 0.2 ng.L-1 for water samples which impose the use of very sensitive analytical techniques to perform such analysis. GC-ICP-MS is the only analytical technique able to achieve such low concentration level, but the expensive equipment requires also qualified personnel to operate, so not all routine laboratories can afford to use it. Preconcentration methods are therefore a good alternative to obtain a more concentrated and cleaner sample extract and later use an easier and affordable analytical technique like GC-MS. In this work, a new method to analyse organotin compounds in water samples using a preconcentration step with polydimethylsiloxane sorbents was developed and validated. The analytical method exhibited linearity higher than 0.9967 for all compounds. For butyltin compounds, LOQ were between 5.7-20.1 pg.L-1 with precision below 8%. For methyltin compounds, LOQ were between 26.9-106 pg.L-1 with precision below 22%. Matrix effects were evaluated for simulated synthetic estuarine and river waters and was then applied to real estuarine and river water samples. Very good recoveries were obtained for butyltins ranging between 87% and 131%. Methyltins, however, exhibited recoveries between 26% and 118% as a result of matrix effect no accurately corrected by the quantification by external calibration.

First record of the green microalgae Coccomyxa sp. in blue mussel Mytilus edulis (L.) from the Lower St. Lawrence Estuary (Québec, Canada)

During autumn 2012 and spring 2013, blue mussels Mytilus edulis (L.) with strongly deformed (L-shaped) posterior shell margins and green spots in soft tissue (microalgae) were collected from intertidal zone along the south shore of the Lower St. Lawrence Estuary near Rimouski (Québec, Canada). Identification of algal cells infesting mussels as Coccomyxa sp. was confirmed by rRNA sequencing and HPLC pigment analysis. Flow cytometric analysis revealed the presence of algal cells in the hemolymph and extrapallial fluid in mussels with deformed and non-deformed shells; concentrations of algal cells were ranged from about 200mL−1 in mussels with actually non-deformed shells to concentrations reaching up to 3.8×107mL−1 in mussels with heavily deformed ones. Chemical analyses of soft tissues led us to conclude that butyltin compounds and trace metals cannot be considered among factors responsible for the shell deformity observed. Using scanning electron microscopy, the biogenic nature of the erosion on the external shell surface and aragonitic lenses of prisms in the curvature zone of deformed shells (in sections) were recorded. The sequence of the green algae from M. edulis of the Lower St. Lawrence Estuary was closely related to Coccomyxa sp. infecting M. edulis from the Flensburg Fjord (North Sea) and Modiolus modiolus (L.) from the Vityaz Bay (Sea of Japan).

Degradation kinetics of butyltin compounds during the bioremediation of contaminated harbour sediments

The present study was aimed at the reclamation of harbour sediments contaminated with butyltin compounds (BTCs) by means of biostimulation and/or bioaugmentation experiments carried out in a 5-L slurry bioreactor. In the biostimulation experiment with inorganic nutrients, almost 50% of TBT was degraded in 20 weeks. In the bioaugmentation experiment with a microbial consortium, no significant degradation of TBT was observed. Conversely, bioaugmentation combined with biostimulation led to a decrease of ∼50% in TBT after four weeks. A simple kinetic model fitted to the experimental data of BTC concentration allowed us to estimate that 10 weeks are needed to decrease BTC contamination by 90% using a strategy based on both biostimulation and bioaugmentation, and 29 weeks for a strategy using biostimulation only. Overall, our study indicates that strategies based on biostimulation coupled to bioaugmentation can be effective in significantly reducing the concentration of BTCs over relatively short timescales.

Organotins pollutions in seawater and sediment around a shipyard

Six organotins including monobutyltin, debutyltin, tributyltin (TBT), monophenyltin, dephenyltin (DBT), triphenyltin were analyzed to investigate a status and effects of a shipyard to organotins pollution in seawater and sediment from 31 sampling sites, in total, in Jinhae Bay. TBT (mean concentration=2.24 ng/L as Cl) and DBT (mean concentration=3.69 ng/L as Cl) were found as two dominant organotins in water samples. In sediment samples, TBT, which has mean concentration of 53.4 ng/g wet weight as Cl and accounted for 74% in total organotins concentration, in average, was consistently found as the predominant organotin. Phenyltins were not found or found as low concentrations comparing with butyltins. Remarkable geographic distribution of TBT and butyltin compounds showed lower concentrations of those compounds in sampling sites located far from the shipyard.

울산만 퇴적물 내 유기주석화합물의 시공간적 분포 특성

Tribuyltin (TBT)을 포함한 유기주석 방오도료의 국내 사용규제에 따른 저감효과를 평가하기 위해서, 국내에서 가장 큰 산업항 중 하나인 울산항 주변에서 2009년과 2011년에 채취한 퇴적물 내 유기주석화합물(butyltin compounds; BTs)을 정량하여 잔류수준과 공간적 분포를 조사하였다. 또한 2003년 조사결과와 비교하여 퇴적물 내 유기주석화합물 잔류의 장기경향을 조사하였다. 퇴적물 내 TBT의 농도범위는 14.2~1204 ng Sn <TEX>$g^{-1}$</TEX> dry wt이었고, dibutyltin은 19.5~980 ng Sn <TEX>$g^{-1}$</TEX> dry wt을 보였다. BTs의 가장 높은 농도는 대형조선소 부근에서 조사되었고, 다음으로 높은 농도는 울산항 컨테이너선 정박지 부근에서 조사되었다. 이것은 울산만에서 TBT의 가장 중요한 배출원은 선박활동을 포함한 해운산업과 관련 있음을 의미한다. 2003년, 2009년, 2011년의 BTs 농도를 비교한 결과, 퇴적물 내 TBT 농도는 유의한 수준으로 감소하고 있어서 국내 사용규제에 따른 저감 효과가 울산만에서도 나타나고 있었다. 해수와 생물내 농도감소는 보고된 적이 있지만, 규제 이후 퇴적물에서 유기주석화합물의 농도감소는 이번 연구에서 처음 보고되는 결과이다. 하지만, 퇴적물 내 BTs의 잔류수준은 생물학적 영향농도보다 높은 수준이었다. 따라서 울산만에서 유기주석화합물로 인한 오염에 대한 저감노력과 지속적인 모니터링이 필요하다. Butyltin compounds (BTs) were determined in surface sediment samples from Ulsan Bay in 2009 and 2011, to assess the contamination status and the effectiveness of tributylin (TBT) restriction of Korea. Dibutyltin and TBT concentrations in sediments in 2011 ranged from 19.5 to 980 and 14.2 to 1204 ng Sn <TEX>$g^{-1}$</TEX> dry weight, respectively. The highest TBT concentration was found in a big shipyard complex and the next highest was found in harbor, suggesting that harbor and shipyard activities are a major contamination source of TBT in Ulsan Bay. Concentrations of BTs in Ulsan Bay sediments were significantly lower in 2009 and 2011 than that in 2003 survey previously reported, probably as a consequence of the legislative action in Korea. However, TBT concentrations in sediments still exceeded ecotoxicological values. Therefore, it will be important to monitor and reduce TBT contamination in sediments until the levels fall well below ecotoxicological levels.

Bioaccumulation of butyltins and liver damage in the demersal fish Cathorops spixii (Siluriformes, Ariidae)

The toxicity of butyltin compounds (BTs), mainly tributyltin (TBT), has been reported in different organisms. However, such an analysis in fish after field exposure with reference to the related biomarkers has not been commonly observed in the literature. This study presents the uptake of BTs in the liver of a neotropical marine catfish Cathorops spixii in Paranagua Bay, an important estuarine system located in southern Brazil. Two different areas, close to and distant from the harbor, were used for chemical analysis evaluation of hepatotoxicity through genetic, enzymatic, and histopathological biomarkers. The presence of polycyclic aromatic hydrocarbons in bile was also considered as a biomarker. The results showed a significant relationship between TBT levels and the inhibition of biotransformation enzymes and high occurrence of melanomacrophages in fish collected close to the harbor site. These effects were linked to the absence of TBT metabolites in the liver. In the second site, the presence of DBT was associated with an increase in EROD and GST activity. The larger amount of DNA damage as well as the highest oxidative stress was noted in fish from the less TBT-polluted area, where DBT and bile PAHs occurred. These findings showed different impact levels due to or increased by the chronic exposure of biota to BTs.

Organotin compounds in surface sediments of the Southern Baltic coastal zone: a study on the main factors for their accumulation and degradation

Sediment samples were collected in the Gulf of Gdańsk, and the Vistula and Szczecin Lagoons—all located in the coastal zone of the Southern Baltic Sea—just after the total ban on using harmful organotins in antifouling paints on ships came into force, to assess their butyltin and phenyltin contamination extent. Altogether, 26 sampling stations were chosen to account for different potential exposure to organotin pollution and environmental conditions: from shallow and well-oxygenated waters, shipping routes and river mouths, to deep and anoxic sites. Additionally, the organic carbon content, pigment content, and grain size of all the sediment samples were determined, and some parameters of the near-bottom water (oxygen content, salinity, temperature) were measured as well. Total concentrations of butyltin compounds ranged between 2 and 182 ng Sn g−1 d.w., whereas phenyltins were below the detection limit. Sediments from the Gulf of Gdańsk and Vistula Lagoon were found moderately contaminated with tributyltin, whereas those from the Szczecin Lagoon were ranked as highly contaminated. Butyltin degradation indices prove a recent tributyltin input into the sediments adjacent to sites used for dumping for dredged harbor materials and for anchorage in the Gulf of Gdańsk (where two big international ports are located), and into those collected in the Szczecin Lagoon. Essential factors affecting the degradation and distribution of organotins, based on significant correlations between butyltins and environmental variables, were found in the study area.Electronic supplementary materialThe online version of this article (doi:10.1007/s11356-013-2115-x) contains supplementary material, which is available to authorized users.

Modulation of the F1FO‐ATPase function by butyltin compounds

Among butyltin compounds, tributyltin (TBT), widely exploited in the past in antifouling paints for its biocidal properties, is long known as one of the most harmful sea contaminants. Among the ascertained and universal toxicity mechanisms, TBT targeting F1FO‐ATPase and thus impairing cell bioenergetics, is here reviewed. While TBT effects on F1FO‐ATPase have been investigated for decades, the possible impact of the derivatives dibutyltin (DBT) and monobutyltin (MBT), produced by abiotic and/or biotic dealkylation of TBT and usually considered far less toxic, have been poorly explored up until now. Butyltin effects on F1FO‐ATPase and their underlying action mechanism seem to be tightly structure dependent. Butyltins are membrane‐active toxicants. Owing to its more pronounced lipophilicity TBT targets the transmembrane FO sector, blocks ionic translocation and causes a dose‐dependent loss of sensitivity to FO inhibitors such as oligomycin and N,N′‐dicyclohexylcarbodiimide. DBT strongly inhibits F1FO‐ATPase activity by competing with the Mg+2 cofactor in the F1 catalytic site but is ineffective on the enzyme sensitivity to FO inhibitors. MBT is apparently ineffective. The possible contribution of DBT to the overall butyltin toxicity on membrane systems may not be neglectable since usually TBT coexists with its derivatives in organotin‐exposed animal tissues. Copyright © 2013 John Wiley &amp; Sons, Ltd.

A candidate reference material ‘Mya arenaria’ for the monitoring of butyltin compounds in mollusks in the marine environment

Most analytical techniques used for the speciation analysis of butyltin compounds in biological tissues usually contain multiple procedures (e. g., extraction, derivatization, separation, preconcentration, determination) which may increase the risk of systematic errors. The use of reference materials (RM) makes it possible to correct most of these errors and improve the validity of quality control. In this study, a new candidate RM for butyltin compounds in mollusks was developed. It was prepared with a mollusk 'Mya arenaria' directly bought from the market. The preparation of this candidate RM, the homogeneity and stability studies, the value assignment and the evaluation of uncertainty were described. The certified values of 0.33 +/- 0.08, 0.62 +/- 0.09, 2.64 +/- 0.20 mu g Sn g(-1) (based on dry mass) for monobutyltin (MBT, [Sn(C4H9)(3+)]), dibutyltin (DBT, [Sn(C4H9)(2)(2+)]) and tributyltin (TBT, [Sn(C4H9)(3)(+)]) respectively have been assigned by inter-laboratory comparison. This work will be of great support to the monitoring of butyltin compounds in biota, as well as meeting the need for implementing international treaties in China.

Differences in bioaccumulation of butyltin compounds between blue mussel, Mytilus galloprovincialis, and green mussel, Perna viridis

Differences in bioaccumulation of butyltin compounds between blue mussel, Mytilus galloprovincialis, and green mussel, Perna viridis

Temporal Trends (2004–2009) of Imposex in Rock Shells Thais clavigera Collected Along the Korean Coast Associated With Tributyltin Regulation in 2003 and 2008

We investigated the temporal trend in contamination of butyltin compounds (BTs) along the Korean coast using imposex and tributyltin (TBT) burden in gastropods (Thais clavigera) as a biomonitor. Thais clavigera were collected from 26 locations with different shipping activities between 2004 and 2009 after restrictions on TBT-based antifouling paints were imposed in Korea. In the present study, imposex indices and TBT tissue concentrations significantly decreased over time from 2004 to 2009, confirming the effectiveness of TBT regulation. However, imposex in 2009 samples was still found. Significantly high imposex indices and TBT tissue residues were found in large ports containing commercial and ferry services compared with small ports and background areas. Imposex indices in background areas had decreased to zero, suggesting recovery from imposex caused by BT contamination. These results suggest that recovery from TBT contamination occurs faster in areas with very low maritime activities than areas with high maritime activities.

Change in Retrospective Butyltin Compounds in Korean Bays

Abstract The use of tributyltin (TBT) has been banned in Korea since 2003. In this study, changes in butyltin compound concentration from 1992 to 2009 were examined by area. The number of ships, which greatly influences butyltin compound contamination, continuously increased, but butyltin compound concentration decreased. Results indicated that the regulation of TBT is effective in Korea. The increase in the concentration was caused by military and coast-guard ships, ballast water, and the illegal use of materials. According to port distribution characteristics along the Korean coasts, the level of butyltin compound contamination was high along the west and south coasts in 1992, whereas it was high along the south and east coasts since 2006. We found that overall butyltin compound concentrations decreased in Korea, but concentrations remained high in some regions.

Accumulation of butyltin compounds in finless porpoises (Neophocaena asiaeorientalis) from Korean coast: Tracking the effectiveness of TBT regulation over time

The concentrations of butyltin compounds (BTs) were measured in the livers of finless porpoises (Neophocaena asiaeorientalis) caught off the Korean coast in 2003 and 2010, to assess the effectiveness of legislative action against BTs. The concentrations of BTs ranged from 65.1 to 1432 (average: 370) ng/g wet weight, within the ranges reported by previous studies. The levels of BTs in almost all the samples exceeded the suggested threshold value, implying potential adverse health effects from the BT exposures. Concentrations of BTs were significantly correlated with body length, weight, and age of finless porpoises, but were not correlated with sex. Spatial differences in the concentrations of BTs were not observed between Yellow and South Seas, while there was a significant decrease in BTs between the sampling years of 2003 and 2010. Our result indicates that the effectiveness on TBT ban has reached to marine mammals in the coastal waters of Korea.

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.

Fate and tidal transport of butyltin and mercury compounds in the waters of the tropical Bach Dang Estuary (Haiphong, Vietnam)

In this work, two field campaigns were performed in July 2008 (wet season) and March 2009 (dry season) to produce original data on the concentration, partition and distribution of mercury and butyltin compounds along the tropical Bach Dang Estuary located in North Vietnam (Haiphong, Red River Delta). The results demonstrate that mercury and butyltin speciation in the surface waters of this type of tropical estuary is greatly affected by the drastic changes in the seasonal conditions. During high river discharge in the wet season, there was a large estuarine input of total Hg and tributyltin, while the longer residence time of the waters during the dry season promotes increasing MMHg formation and TBT degradation. Although most of the Hg and TBT is transported into the estuary from upstream sources, tidal cycle measurements demonstrate that this estuary is a significant source of TBT and MMHg during the wet (∼3kgTBT/day) and dry (∼3gMMHg/day) seasons.

In situ experiments for element species-specific environmental reactivity of tin and mercury compounds using isotopic tracers and multiple linear regression

The fate of mercury (Hg) and tin (Sn) compounds in ecosystems is strongly determined by their alkylation/dealkylation pathways. However, the experimental determination of those transformations is still not straightforward and methodologies need to be refined. The purpose of this work is the development of a comprehensive and adaptable tool for an accurate experimental assessment of specific formation/degradation yields and half-lives of elemental species in different aquatic environments. The methodology combines field incubations of coastal waters and surface sediments with the addition of species-specific isotopically enriched tracers and a mathematical approach based on the deconvolution of isotopic patterns. The method has been applied to the study of the environmental reactivity of Hg and Sn compounds in coastal water and surface sediment samples collected in two different coastal ecosystems of the South French Atlantic Coast (Arcachon Bay and Adour Estuary). Both the level of isotopically enriched species and the spiking solution composition were found to alter dibutyltin and monomethylmercury degradation yields, while no significant changes were measurable for tributyltin and Hg(II). For butyltin species, the presence of light was found to be the main source of degradation and removal of these contaminants from surface coastal environments. In contrast, photomediated processes do not significantly influence either the methylation of mercury or the demethylation of methylmercury. The proposed method constitutes an advancement from the previous element-specific isotopic tracers' approaches, which allows for instance to discriminate the extent of net and oxidative Hg demethylation and to identify which debutylation step is controlling the environmental persistence of butyltin compounds.

Distribution of Antifouling Biocides and Perfluoroalkyl Compounds in Sediments From Selected Locations in Indonesian Coastal Waters

Coastal marine environments are considered to be the most sensitive areas for the accumulation of organotin (OT) compounds and other emerging new pollutants, such as perfluoroalkyl compounds. Contamination by these compounds is a matter of great concern due to their accumulation and possible negative impact on the coastal environment and organisms. The concentrations of tributyltin (TBT) compounds were greater in Indonesia, i.e., on the order of Bitung > Manado > Jakarta Bay > Gangga Island, and TBT in sediment from Bitung and Manado was the dominant species among butyltin (BT) compounds. Sea Nine 211, diuron, and irgarol 1051 were detected among alternative biocides in Bitung, Manado, and Gangga Island and irgarol 1051 was detected in Jakarta Bay. Perfluorooctanoic acid (PFOA) and perfluorosulfonic acid (PFOS) in Jakarta Bay were detected at 0.25 to 6.1 μg kg(-1) dry weight (dw) and 0.58 to 3.7 μg kg(-1) dw, respectively, and the concentrations of PFOS at most sampling sites were greater than those of PFOA. Thus, coastal waters from Indonesia have already been contaminated by antifouling biocides and perfluoroalkyl compounds.

Preparation of a sewage sludge laboratory quality control material for butyltin compounds and their determination by isotope-dilution mass spectrometry

The characterisation of a laboratory quality control material (QCM) for dibutyltin (DBT) and tributyltin (TBT) in sewage sludge is described. The reference values were determined by the use of two different types of isotope-dilution mass spectrometry: gas chromatography-mass spectrometry and gas chromatography-inductively coupled plasma mass spectrometry. To avoid possible analytical errors such as non-quantitative extraction and species degradation during sample preparation, different extraction methods were tested (microwave- and ultrasound-assisted extraction and mechanical stirring). The reference values were based on the unweighted means of results from the homogenisation and characterisation studies. The reference values obtained were 1,553 ± 87 and 534 ± 38ng Sn g(-1) for DBT and TBT, respectively. In the uncertainty budget estimation, the sample inhomogeneity and between-method imprecision were taken into account. The concentrations of DBT and TBT in QCM are similar to those in the harbour sediment certified reference material PACS-2. Likewise, the levels of DBT and TBT are in the range of these compounds normally present in sewage sludge worldwide. In the future, the QCM will be used for an intercomparison study on DBT and TBT in sewage sludge, and as a day-to-day QCM during studies concerning the application of sewage sludge as an additive to artificial soil or as a raw material in civil engineering construction.