Bioaccumulation of organotin compounds in the marbled electric ray (Torpedo marmorata) in the northern Adriatic Sea.

Organotin compounds (OTC), tri-, di- and monobutyl tin, were determined in the tissues of marbled electric ray (Torpedo marmorata) in the Adriatic Sea. Marbled electric ray specimens were provided by local fishermen from three localities in the northern Adriatic: area close to the shipyard in Seca, the natural protected area Strunjan Nature Reserve and along the west Istrian coast. To assess the concentration of OTC in the environment, sediment samples were also analysed. After an adequate extraction of OTC from both matrices, their concentrations were determined by GC-ICP-MS. The results indicate that the accumulation of TBT (tributyltin) and DBT (dibutyltin) in the marbled electric ray is related to the possible pollution sources, since their total concentrations were significantly higher (p < 0.001) in the area close to the shipyard (up to 69 µg Sn kg-1, w.w.) in comparison to the other two areas less affected by direct pollution (up to 7 µg Sn kg-1, w.w.). TBT concentrations ranged from 2 to 42 µg Sn kg-1, w.w., DBT concentrations were in the range from 2 to 22 µg Sn kg-1, w.w., and MBT concentrations were mostly below the detection limit with the highest up to 4 µg Sn kg-1, w.w. The proportion of the three determined congener concentrations in sediment samples indicate a temporally older pollution with these compounds, with prevailing DBT and MBT concentrations up to 30 µg Sn kg-1, w.w., and much lower TBT concentrations up to 7 µg Sn kg-1, w.w. According to our results, marbled electric ray could be considered as an ideal bioindicator of environmental pollution due to its ecological characteristics.

Update on the status of the contamination by organotin compounds in sediment of Nuevo Gulf, Argentina. Insights from field and experimental studies.

Organotin compounds are persistent pollutants and are considered chemicals of high environmental concern. In the present study, the distribution and degradation of tributyltin were evaluated in field sediments and through an ex situ experiment. For this, sediment samples from two locations were analysed: Luis Piedrabuena Harbour, with higher maritime traffic, and Cerro Avanzado, which receives less impact from anthropogenic activities. The results indicated that pollution levels at Luis Piedrabuena Harbour have decreased compared with studies performed 9 years ago for the same area. On the contrary, traces of organotin compounds have been found for the first time at Cerro Avanzado. Moreover, the butyltin degradation index indicated that organotin compounds undergo an advanced degradation process in the collected samples at both sites. Ex situ experiments revealed a limited capacity of sediments to retain tributyltin, and suggested an active role of bioturbation activity in the degradation of these compounds. In addition, visualisation using chemometric techniques (principal components analysis) allowed a simpler analysis of two sediment characteristics: the degree of contamination and the degradation levels of organotin compounds.

First assessment of butyltins (BuTs) contamination of the Montenegrin coast (Southeast Adriatic): Tributyltin (TBT) poses a threat to the marine ecosystem.

This study presents the first assessment of butyltins (BuTs) pollution of the Montenegrin coast. The distribution of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) was investigated in mussels, sediments and water overlying sediment after the sediment resuspension. The results showed that the investigated sites (marinas, ports, shipyards) are contaminated with BuTs (19-402 ng (Sn)/g in mussels; 43-20,641 ng (Sn)/g in sediments; 9-566 ng (Sn)/L in overlying waters). The measured TBT concentrations indicate that toxic effects on marine organisms are expected at most locations. The simultaneous analysis of BuTs and total Sn in sediment cores allowed the assessment of TBT historical input, while it was demonstrated that resuspension of contaminated sediments leads to the release of all BuTs into the water column. This study shows that, despite the ban of TBT-based antifouling paints more than a decade ago, pollution of the marine environment with TBT is still a problem and regular monitoring remains essential.

Quantification of tributyltin in seawater using triple isotope dilution gas chromatography-inductively coupled plasma mass spectrometry achieving high accuracy and complying with European Water Framework Directive limits.

A triple isotope dilution GC-ICPMS method for the determination of tributyltin (TBT) was developed and validated to meet the European Water Framework Directive (WFD) requirements. The validation procedure involved the evaluation of trueness, precision (repeatability, intermediate precision), limit of detection (LOD) and limit of quantification (LOQ), stability, measurement uncertainty and traceability studies. The method is one of the most sensitive methods published to date with good accuracy, 103% average recovery in the range with %RSDs of 2.8-6.7%. A LOD value of 0.015 ng L-1 for the TBT cation was achieved with a sample volume of 12 mL seawater. TBT was derivatized using 20 µL sodium tetraethylborate solution (0.05% NaBEt4) to make volatile for GC-ICPMS. Measurement uncertainty was in the range of 4.8-13% which was achieved through dissolution of tributyltinchloride (TBTCl) in 1-propanol, a low-volatility solvent combined with the use of a triple isotope dilution (ID) calibration technique. Isotope dilution calibration was performed by adding 117Sn isotopically enriched TBT to the seawater samples. The stability test results showed that TBT concentration was stable for three months in seawater samples after passing through a 0.2 µm filter and stored in amber glass bottles at 4°C. The response surface methodology (RSM) approach was successfully implemented to provide optimal conditions for large volume injection (LVI) to obtain the maximum analytical signal. The key variables selected in the experimental design were evaporation time, evaporation temperature, carrier flow, and injection speed. This method was applied to seawater samples collected from the Bay of Izmit, Kocaeli, Turkey, where TBT pollution has not been measured yet.

Development and Application of a Novel QuEChERS Method for Monitoring of Tributyltin and Triphenyltin in Bottom Sediments of the Odra River Estuary, North Westernmost Part of Poland.

A Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) extraction method combined with Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) for determination of organotin compounds (OTC) has been newly developed. The novel analytical method was validated and the quality of the results was tested by the use of certificate reference material of freshwater sediment BCR 646. The method was applied in determination of OTC concentration in real samples of bottom sediments collected from the Polish part of Odra River Estuary. The samples came from locations with different anthropogenic impact. Additionally, the extraction recovery of OTC and matrix effect on MS signal response was investigated based on those real environmental samples. It was found that organic compounds and anthropogenic contaminations present in bottom sediments may affect extraction efficiency of the organotin compounds (OTC) and change the matrix effect on MS signal response. The highest concentrations of tributyltin were found in bottom sediments collected from locations in vicinity of the Szczecin harbor and shipyards. The presence of triphenyltin above limit of detection (5 ng TPhT/g of sediment) was observed only in two samples and its concentration was several times lower compared to concentration of tributyltin (from 58 ng/g to 5263 ng/g). In spite of the fact that, the application of TBT-based paints on hull of vessel entering EU ports has been banned by European Commission regulation No. 782/2003 since 2008, the OTC compounds are still present in bottom sediment and pose significant threat to the environment. This threat should be taken into account during dredging of waterways and other hydrotechnical works.

[Determination of Tributyltin and Triphenyltin in Fish and Shellfish Using Accelerated Solvent Extraction and Liquid Chromatography with Tandem Mass Spectrometry].

A determination method for tributyltin (TBT) and triphenyltin (TPT) in fish and shellfish using an accelerated solvent extractor (ASE) and LC-MS/MS was developed. The chromatographic separation was conducted on a Poroshell 120 EC-C18 column using an isocratic mobile phase of 0.1% formic acid in 70% methanol. Sample preparation was performed using ASE at 125℃ with n-hexane and a cleanup using a Florisil cartridge. Internal calibration curves using deuterium-labeled TBT and TPT were employed for quantification. For both TBT and TPT, the calibration curves were linear in the range of 0.2-250 ng/mL, and the method quantification limits were 0.8 ng/g for both TBT and TPT. A National Institute for Environmental Studies certified reference material, No. 15 (adductor muscle of scallop), was analyzed to assess the performance of the developed method. The trueness, relative standard deviations of repeatability, and within laboratory reproducibility of this method, evaluated using a recovery test with four spiked fish species and one shellfish, ranged from 89.3 to 105.3%, 1.0 to 4.5%, and 1.3 to 7.6%, respectively.

Assessing the Efficacy of a Sediment Remediation Program Using Benthic and Pelagic Copepod Bioassays.

Tributyltin is an organotin chemical that has been commonly used in ship antifouling paints. Despite the global total prohibition of tributyltin-based paint in 2008, tributyltin continues to be found at toxic levels in areas of high maritime traffic such as ports and harbors. A remediation program was conducted at a New Zealand port to reduce tributyltin and copper concentrations to acceptable values. The present study assessed the efficacy of the program using a combination of chemical analyses and copepod bioassays. Sediment and water samples were collected at 3 locations along a spatial gradient within the port, and concentrations of various organotin compounds and trace metal levels were measured pre- and postremediation. The toxicity of sediment and elutriate samples was estimated by benthic and pelagic copepod bioassays. Although acute toxicity in sediment samples was reduced following remediation, reproductive success was still affected for the benthic copepod. This approach combining chemical analysis and bioassays is promising for assessing the efficacy of remediation processes at contaminated marine sites. Environ Toxicol Chem 2020;39:492-499. © 2019 SETAC.

Organotin compounds in touristic marinas of the northern Adriatic Sea: occurrence, speciation and potential recycling at the sediment-water interface.

Butyltin compound (BTC) contamination was evaluated in two north Adriatic marinas, San Rocco (Italy) and Lucija (Slovenia). BTC sedimentary concentrations (121 ± 46 and 352 ± 30 ng Sn g-1 in San Rocco and Lucija, respectively) evidenced the past use of antifouling paints, confirmed by the reduced tributyltin content (~ 46%) with respect to the sum of BTC. Elemental and organic carbon isotopic (δ13C) analyses of bulk sediments and its lipid and humic substances were performed in order to evaluate their role in BTC partitioning and preservation. The δ13C of sedimentary bulk and refractory organic matter suggested that diagenetic processes could play a role in the preservation or release of pollutants. No contamination was found in water collected from the benthic chamber and thus, fluxes at the sediment-water interface were not assessed, except for MBT efflux at Lucija (28.9 ng Sn m-2 day-1). Nevertheless, BTC concentrations in porewaters (up to 75 ng Sn l-1) and rather low sediment-porewater partitioning coefficients (Kd) with respect to the data reported in the literature would suggest a potential risk of the reintroduction of BTC into the water column at both sites: at Lucija, sedimentary contamination is high despite the greater Log Kd, whilst at San Rocco, the low BTC concentration is associated with a reduced sediment affinity.

Butyltins in sediments from the Southern Baltic coastal zone: Is it still a matter of concern, 10 years after implementation of the total ban?

The study was done to assess butyltin contamination in sediments of the Southern Baltic coastal zone, ten years after implementation of the total ban on harmful organotin use in antifouling paints. Sediment samples were collected from two seaports of international significance: the Port of Gdansk and the Port of Gdynia, as well as from the Szczecin Lagoon which plays a significant role as a shipping route connecting the Port of Szczecin with the Port of Swinoujscie. Total concentrations of butyltins in the sediment samples ranged between 5.7 and 3321 ng Sn g-1 d.w. Eighty percent of the samples were found as highly and grossly contaminated with tributyltin. The results were compared with those recorded ten years ago. Despite the improvement, the butyltin contamination still gives rise to concern in the study area. According to the HELCOM recommendation, all samples exceeded the Good Environmental Status boundary for tributyltin in sediments.

On the effectiveness of tributyltin ban: Distribution and changes in butyltin concentrations over a 9-year period in Klaipeda Port, Lithuania.

This study provides an insight on a long-term butyltin pressure, spatio-temporal changes and current tributyltin distribution in the Klaipeda Port sediments. Moreover, it examines whether the restrictions on tributyltin use led to a decreased pollution in the area. Changes over a 9-year period in tributyltin and its metabolites concentrations were analyzed in surface sediments from semi-enclosed bays of the Port. Reduction in organotin level was observed after tributyltin ban came into force: tributyltin concentration reached 3000 ng Sn g-1 d.w. in 2005 whereas 1793 ng Sng-1 d.w. was found to be the highest tributyltin concentration in 2013. The highest contamination was detected in the zones with ship maintenance activity. As late as in 2013, the latter areas still exhibited fresh tributyltin input while the progress of organotin degradation has been observed for other sampling stations along the Port.

Paper Based Photoluminescent Sensing Platform with Recognition Sites for Tributyltin.

In this study, a novel photoluminescence material for the detection of tributyltin (TBT) was developed by using a paper-based nanocomposite system. For this purpose, molecularly imprinted polymeric nanoparticles (MIN) were synthesized with mini-emulsion polymerization technique. Graphene quantum dots obtained by the hydrothermal pyrolysis were immobilized to the nanoparticle surface via EDC-NHS coupling. The fabrication of sensing platform for TBT can be divided into two steps that are the preparation of nanocomposite and the applying the nanocomposite onto nitrocellulose membrane. The selectivity constant and association kinetics were calculated to analyze the interaction of TBT with immobilized MINs. The results proved that the developed nanosensor is promising for the determination of TBT with high selectivity and sensitivity reaching a detection limit of 0.23 ppt in seawater. This novel photoluminescent nanosensor has the potential to pave the way for further studies and applications.

Preliminary studies about the role of physicochemical parameters on the organotin compound dynamic in a South American estuary (Bahía Blanca, Argentina).

This work provides a preliminary study of the destination, mobility, and availability of tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) in contaminated sediments and water column within Puerto Rosales Port, located in the middle zone of the Bahía Blanca Estuary (Argentina). Therefore, this study presents the first comprehensive results of the role of several physicochemical parameters (temperature, pH, Eh, salinity, turbidity, organic matter, chlorophyll, and macronutrients) in behavior of organotin compounds (OTCs) in a marine-coastal ecosystem. The samples were collected seasonally in May, August, and November during 2014. Levels of OTCs were determined in sediments and water column samples by means of gas chromatography-mass spectrometry analysis. Degradation index analyses suggested not recent inputs of TBT at the area of study. However, results submitted a continuous input of TBT into the column water; further, its distribution and degradation pattern were shown to be influenced by salinity, turbidity, particulate organic matter, chlorophyll, and nitrates. These last two parameters, chlorophyll and nitrates, also were very important for sediment samples. Chlorophyll together with high temperatures recorded in the surface sediments triggers biodegradation process of TBT and DBT resulting in high MBT levels while nitrates seemed to promote debutylation process. Furthermore, pH appeared to influence drastically the adsorption/desorption activity of TBT and DBT in sediment. Finally, the Eh obtained suggested a degradation of TBT thanks to the presence of Fe (III) in this compartment. In addition, in fact, the results outlined a possible MBT additional input that contributes to the pollution observed in the study area. Graphical abstract Organotin compounds behavior according to several physicochemical parameters.

Levels and trends of tributyltin (TBT) and imposex in dogwhelk (Nucella lapillus) along the Norwegian coastline from 1991 to 2017.

The banning of organotin biocides, such as tributyltin (TBT), from use in marine antifouling paints is now leading to reproductive health recovery in marine gastropod populations all over the world. TBT induces so-called imposex (superimposition of male sexual characters onto females) in certain marine gastropods, such as the common dogwhelk Nucella lapillus. In this publication, the results of the Norwegian TBT and imposex monitoring in N. lapillus from the period 1991-2017 are presented. Significantly higher levels of TBT and imposex were measured in coastal areas close to shipping lanes along most of the coast prior to 2008 than afterwards. Levels started declining after restrictions were imposed on the use of TBT in all antifouling paint applications, with a total ban in 2008. In 2017, no sign of imposex was found in N. lapillus in any of the monitoring stations along the Norwegian coastline. Based on monitoring data shown herein, the importance of long-term biomonitoring and international chemical regulations, as well as the TBT and imposex story in general, are discussed.

Organotins in the aquatic media of secondary anabranches in the Three Gorges Reservoir Region, China.

The Three Gorges Reservoir Region (TGRR) is one of the most sensitive areas of ecological environment in China. As vital backwater areas, the secondary anabranches of the TGRR were prone to eutrophication in Spring which would affect the distribution and transfer of organotins (OTs) among aquatic media. This study quantified the concentrations of butyltins (BTs) and phenyltins (PhTs) in water columns and aquatic media of two anabranches of the TGRR, the Daning River (DR) and the Xiaojiang River (XR) during the state of eutrophication. Our results showed that the average concentrations of BTs and PhTs in surface water are 43.91, 81.25 ng Sn L-1 in the DR, and 63.49, 69.21 ng Sn L-1 in the XR, respectively, and there were no obvious differences in the concentrations of BTs and PhTs across the water columns in the DR and XR. PhTs, especially monophenyltin (MPhT), are predominated in the dissolved phase, whereas BTs, especially dibutyltin (DBT), are predominated in both suspended particulate matter (SPM) and the sediment. Shipping and agricultural activity were likely the sources of OTs in both the DR and XR. High concentrations of tributyltin (TBT) and triphenyltin (TPhT) are still present in the aquatic media of the TGRR, and pose a significant risk to aquatic organisms due to the potential for bioaccumulation. Therefore, it is necessary to further monitor and assess OTs especially PhTs in surface water, and to continue to restrict the use of OTs to protect the aquatic environment of the TGRR.

A Validated Routine Method for Butyltin Determination in Seafood by Gas Chromatography Inductively Coupled Plasma Isotope Dilution Mass Spectrometry.

Organotin compounds are anthropogenic metal species with multiple uses as pesticides, preservatives, antifouling agents, biocides, and catalysts. Butyltins are the main organotin compounds found in biota, and the highest levels are found in marine foodstuffs. In this paper, we present the figures of merit for an in-house validated method for routine analysis of butyltins in seafood using GC inductively coupled plasma isotope dilution MS. The working range of the method spanned several orders of magnitude from 3.3-1013, 2.4-785, and 0.3-900 ng Sn/g dry weight for monobutyltin (MBT), dibutyltin (DBT), and tributyltin (TBT), respectively. The trueness of the method was evaluated by analyzing Certified Reference Materials (CRMs) ERM CRM 477 (Mussel Tissue) and NIES CRM 15 (Scallop). Recoveries, with RSD % in parentheses, were 78 (±14), 80 (±6), and 88% (±8%) for MBT, DBT, and TBT in ERM CRM 477 and 96% (±5%) for TBT in NIES CRM 15. Good agreements were found between experimental uncertainties and uncertainties predicted for single-laboratory validated methods calculated from the maximum standard measurement uncertainty function. The method has proven to be robust, and the wide range of seafood validated ensures that the method is applicable for measuring butyltins in marine tissue.

Imposex assessment and tributyltin levels in sediments along the Atlantic coast of South Africa.

Female marine gastropods develop imposex (growth of penis/vas deferens) when exposed to TBT (tributyltin). Ours, is the first report of an imposex survey associated with TBT in sediment along 920 km of South Africa's Atlantic coastline. We sampled and analysed 1389 individuals of 13 caenogastropod species, and sediment samples from 25 sites, presumed impacted and not impacted by TBT pollution. Imposex was detected in six species not previously reported to suffer from this phenomenon, at eight sites, with up to 100% of females affected. Butyltins were found at quantifiable concentrations at four sites, with TBT and DBT (dibutyltin) concentrations in sediments up to 20 000 µg/kg dry mass (dm) and 3740 µg/kg dm, respectively. These findings are of major concern considering that TBT has been banned globally since 2008 by the International Maritime Organisation (IMO) - more extensive research is required in areas affected by TBT and where aquaculture is present.

Parental diet affects embryogenesis of the great pond snail (Lymnaea stagnalis) exposed to cadmium, pyraclostrobin, and tributyltin.

Diet quality has a strong impact on life-history traits, but it is not usually considered as a factor in toxicity tests. The purpose of the present study was to evaluate how diets differing in nutritional content affect sensitivity to cadmium, pyraclostrobin, and tributyltin in Lymnaea stagnalis offspring. Three groups were fed a different diet each: lettuce, high-caloric pellets, or a combination of both. Snails fed pellets and both diets had similar growth; however, snails fed lettuce showed lower growth until the fourth month. Egg masses were collected from adult snails fed each diet and exposed to 3 concentrations of either cadmium, pyraclostrobin, or tributyltin. We quantified time to hatch, hatching success, and the developmental stages of embryos. We measured fecundity in adults and total lipids, carbohydrates, and proteins in adult snails and egg masses. Adult snails fed different diets produced a similar number of egg masses, but the number of eggs per egg mass in snails fed pellets was lower than for snails fed the other 2 diets. We found that adult snails fed pellets had a higher lipid content compared to snails fed the other 2 diets. However, egg masses from parental snails fed pellets did not hatch, including those from the controls. Interestingly, egg masses exposed to the lowest concentration of tributyltin had low hatching success. These observations on offspring performance suggest that there are important diet effects that can strongly influence responses that could be diet- and chemical-dependent. Environ Toxicol Chem 2018;37:2428-2438. © 2018 SETAC.

TBT is still a matter of concern in Peru.

Tributyltin (TBT) environmental concentrations as well as imposex levels have been declining in several coastal areas worldwide. However, recent studies have shown that TBT contamination is still an important issue along some Latin American coastal areas. Thus, the incidence of imposex and butyltin compounds (BTs) in sediments and gastropod tissues was spatially and temporally (2009 and 2012) appraised in Lima (Peru) along potential TBT sources (harbors and marinas). Despite the general pattern of reduction close to Callao harbor, a clear increment in the levels of imposex (RPLI = 0.0 to 8.4 and 0.0 to 28.4/VDSI = 0.0 to 3.3 and 0.0 to 3.5) and TBT in tissues (25 to 112 and 62 to 146 ng Sn g-1) of Thaisella chocolata were seen from 2009 to 2012 in two sampling sites, respectively, located nearby a newly established marina. Thus, despite the international restrictions on the use of TBT-based antifouling paints are apparently reducing the inputs at international harbors, the present study clearly shows that marinas are still acting as important sources of TBT to the study area due possibly to the lack of legal restrictions on production, trading and/or use of TBT. The present findings reinforce what has been seen along many other Latin American coastal areas.

Microbes a Tool for the Remediation of Organotin Pollution Determined by Static Headspace Gas Chromatography-Mass Spectrometry.

Tributyltin (TBT) is one of the most toxic anthropogenic compounds introduced into the marine environment. Despite its global ban in 2008, TBT is still a problem of great concern due to its high affinity for particulate matter, providing a direct and potentially persistent route of entry into benthic sediments. Bioremediation strategies may constitute an alternative approach to conventional physicochemical methods, benefiting from the microorganism's potential to metabolize anthropogenic compounds. In this work, a simple, precise and accurate static headspace gas chromatography method was developed to investigate the ability of TBT degrading microbes in sedimentary microcosms over a period of 120 days. The proposed method was validated for linearity, repeatability, accuracy, specificity, limit of detection and limit of quantification. The method was subsequently successfully applied for the detection and quantification of TBT and degradation compounds in sediment samples on day 0, 30, 60, 90 and 120 of the experiment employing the principles of green chemistry. On day 120 the concentration of TBT remaining in the microcosms ranged between 91.91 ng/g wet wt for the least effective microbial inoculant to 52.73 ng/g wet wt for the most effective microbial inoculant from a starting concentration of 100 ng/g wet wt.

First assessment of the effectiveness of the international convention on the control of harmful anti-fouling systems on ships in Tunisia using imposex in Hexaplex trunculus as biomarker.

The global ban on the use of tributyltin (TBT) forced in September 2008 was ratified in Tunisia as late as June 2011. In this context, the present study aims to highlight the consequences of TBT contamination by monitoring 22 Tunisian sites before (2007) and after the ban (2012 and 2016) using as biomarker the occurrence of imposex in Hexaplex trunculus. From 2004 to 2016, complete recovery from imposex was reported in 11 sites. All average imposex indices calculated for each sampling year also decreased: imposex incidence from 61 to 27%, VDSI from 2 to 0.7, and RPLI from 15.7 to 1.6%. Ecological Quality Ratios (EQR) revealed that the sampling sites are in moderate to good ecological status. Overall, the present study confirms the effectiveness of the enacted legislation in reducing the impact of TBT pollution along the Tunisian coast.