Butyltin Concentrations Research Articles

On the effectiveness of tributyltin ban part II: Temporal and spatial trends of organotin pollution in intense sediment accumulation areas and dumping sites of the Baltic Sea

Based on the knowledge gained from our previous study, our aim is to observe the current levels of butyltin (BTs) pollution, changes during different seasons, and the factors that affect these trends in the areas of highest concern. These areas include semi-enclosed bays in the Port that were previously affected by large tributyltin (TBT) inputs, as well as the dumping sites of dredged sediment in the Baltic Sea. Compared to previous studies, there has been a significant decrease in the levels of BTs in the Klaipeda Port. However, the sediment in the semi-enclosed bays still contained BTs, ranging from less than 0.5 ng Sn g−1 dw to as high as 728.5 ng Sn g−1 dw. Some BTs were also detected in the currently exploited dumping sites of the Baltic Sea. Moreover, butyltin degradation index (BDI) revealed occasional fresh TBT input or slow degradation both in the Port and in the Sea. Some trends in butyltin concentrations were indicative of the impact of climate change in Lithuania, which are consistent with global trends. We also found that variations in BTs concentrations were closely related to dredging and cleaning activities taking place in the Klaipeda Port. Correlation, principal component, and cluster analysis revealed close relationship between TBT and its degradation products, as well as between TBT and Zn, Pb, Cu. Ship cleaning/maintenance activities were identified as the main source of pollution in the study area. Despite the gradually decreasing BTs concentration in the Klaipeda Port, the problem is not yet completely solved.

Concentrations of organotin compounds in aquatic biota in coastal waters of Johor, Malaysia

AbstractThe concentrations of organotin (OT) compounds, butyltin (BT) and phenyltin (PT), in aquatic organisms from Merambong and Tinggi Island, Malaysia, which differ in industrial and economic activities, were measured. Tributyltin (TBT) compounds among BTs ranged from 2.9–28 and <0.1–21 ng g−1 ww in aquatic organisms from Merambong and Tinggi Island, respectively. Triphenyltin (TPT) compounds among PTs ranged from <0.1–25 ng g−1 ww and <0.1–61 ng g−1 ww in aquatic organisms from Merambong and Tinggi Island, respectively. A survey of OT concentrations among the species of OT compounds revealed that the concentrations of BTs and PTs in crabs and clams were high while those in fish were low. Correlation analysis with stable nitrogen isotopes suggest that OT compounds did not accumulate in aquatic organisms through the food web. The measurement of OT compounds in tissues and organs of fish revealed that BT concentrations in liver were higher than those in muscle and that BTs were detected in eggs of fish.

Butyltin Contamination in Fishing Port Sediments after the Ban of Tributyltin Antifouling Paint: A Case of Qianzhen Fishing Port in Taiwan

This study investigated the concentrations of monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT) in the sediments of the Qianzhen Fishing Port (Taiwan) in 2020. Further, the pollution status, composition, and potential ecotoxicity of BTs were evaluated. This case study provides a reference for the benefits of the ban of TBT-based antifouling paint to date. Results showed that the total butyltin (ΣBTs, sum of TBT, DBT, and MBT) concentrations measured in the sediments of the Qianzhen Fishing Port ranged between 14.2–807 ngSn·g−1 dw, with an average of 356 ± 305 ngSn·g−1 dw. TBT was the most dominant species, with an average concentration of 303 ± 287 ngSn·g−1 dw. This average TBT concentration is about 4.3 times lower than in 2003, showing the progress of gradual degradation of TBT in the sediments. Still, the degradation is rather slow, with a half-life of about 8.09 years. An analysis of the effects of TBT on organisms in the sediments of the Qianzhen Fishing Port was carried out according to the TBT toxicity guidelines of the US Environmental Protection Agency and the assessment class criterion for imposex (ACCI) of the Oslo and Paris Commission (OSPAR). The results showed that TBT levels in 80% of the sediments may pose negative effects on sensitive gastropods, and half of the sediments may even have an impact on gastropod reproduction. These show that marine life is still affected and threatened by TBT compounds, despite the decline of TBT concentrations since the ban of TBT-containing antifouling paints on ships in 2008. Therefore, it is necessary to continue paying attention to the changes of TBT concentrations and their potential ecological risks in the marine environment, and to formulate TBT management plans and strategies to mitigate their impacts in marine ecosystems.

Long-term monitoring of Nucella lapillus imposex in Ria de Aveiro (Portugal): When will a full recovery happen?

Nucella lapillus imposex has been monitored in Ria de Aveiro (Portugal) in order to understand the evolution of organotin (OT) pollution after the EU ban on OT-based antifouling systems (OT-AFS). A rapid decrease of imposex occurred, but a countercurrent tendency upsurged recently (2018–2019) with a slight increase of imposex at some sites, instead of a continuous decline towards a complete recovery. In 2018 the vas deferens sequence index ranged between 0.6 and 1.0 across stations and the percentage of females with imposex varied from 63 to 100%. In 2019 these parameters varied between 0.4 and 1.0 and 37–100%, while the concentration of butyltins (TBT, DBT, MBT) in the dogwhelk tissues were < 1 ng Sn g-1 dw. Although N. lapillus imposex levels are low they are indicative of OT pollution. The full recovery of N. lapillus imposex in the future is uncertain and a cause for concern.

Spatial distribution of butyltins and imposex in eastern Brazilian Amazon

Spatial distribution of Butyltins (BTs) in surface sediments and gastropod tissues were quantified, with samples taken from an estuarine system of the Eastern Amazon, Brazil. The imposex incidence was also assessed using Thaisella coronata (Gastropoda, Mollusca). The sediment sampling was carried out at 19 sites and T. coronata in 6 of those. The highest BTs levels were detected in sediments of a Marine Extractive Reserve (27.1 ng Sn g−1) and in an urban area (19.8 ng Sn g−1). In T. coronata tissues, BTs levels ranged from <5 to 142 ng Sn g−1. Imposex incidence ranged from 0% to 100% and VDSII (penile papillae) was registered in gastropods from 5 out of 6 sampled sites. The results suggest that BTs concentrations are related to sampled area use, but also to the local hydrodynamics, highlighting the importance of an effective control in the use of TBT-based antifouling paints in the Eastern Amazon.

Accumulation of butyltin compounds in the pantropical spotted dolphin, Stenella attenuate, from the coasts of Taiwan

Butyltin compounds (BTs), including mono- (MBT), di- (DBT) and tributyltin (TBT), were identified in the pantropical spotted dolphin, Stenella attenuate, from the coasts of Taiwan. In all 13 cases, the muscle tissues were analyzed. But the liver content was only measured in one of the samples. Dolphin muscle contained BTs ranging from 14 to 202 ng/g wet wt, with MBT dominant in the samples. Sex-differential and age-dependent accumulations of BTs in muscle were not found. The concentration of BTs in the liver was 701 ng/g wet wt, and MBT was dominant (77%). In general, butyltin concentrations in dolphins from the coastal waters of Taiwan are within the range of cetaceans reported worldwide. And to our knowledge, this is the first study reporting on the butyltin pollution of marine mammals in Taiwan.

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

This study provides an insight on a long-term butyltin pressure, spatio-temporal changes and current tributyltin distribution in the Klaipėda 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.

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 Gdańsk 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 Świnoujście. 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.

A review of organotin contamination in arctic and subarctic regions

Abstract Organotin (OT) compounds are of continued Arctic concern as they are still widely used despite the most well-studied OT, tributyl tin (TBT), being restricted from use on marine vessels to prevent fouling by marine organisms. The highest OT concentrations found in Arctic fauna are in regions associated with human activity especially shipping. There is an overall trend of declining butyl tin (BT) concentrations in Arctic fauna especially molluscs which are the subject of a limited number of long-term monitoring studies. The incidence of imposex has likewise generally declined in molluscs in response to declining TBT concentrations. There are a number of knowledge gaps in OT occurrence and transport in the Arctic that warrant continued monitoring. OTs, in particular octyl tins, are heavily used in the production of plastic, hence leaching from plastic may be an unrecognized source to Arctic regions. This review also found several studies reporting volatile tin species in the atmosphere suggesting atmospheric transport of volatile tins to the Arctic is possible. Relative to other more well know persistent organic pollutants, there are few reports of OTs in marine mammals and temporal tend studies are needed to define trends in BTs and search for the occurrence of other tin species.

Distribution of butyltins at dredged material dumping sites around the coast of China and the potential ecological risk

Previous research has found butyltin pollution at dumping sites, which are the final fate of dredged material mostly originating from harbors and navigation systems. The distribution and impacts of butyltins were assessed in sediments at 12 dumping sites of China. Total butyltins (monobutyltin, dibutyltin, and tributyltin) concentrations ranged from 1.76 to 486.62 ng Sn g−1 dw. This study also presents evidence of considerable historic inputs of tributyltin (TBT) to Dumping sites 01, 05, 06, 08, 09 and 11, with evidence of heavier recent TBT input at Dumping site 04 and 10. The butyltin contamination at dumping sites was comparatively light and historic compared to research in other countries, but was more serious than other sea regions. TBT levels at Dumping site 09 probably have negative effects on biological systems. Overall, more attention should be paid to the level and impacts of butyltins in the sediment at dumping sites in China.

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.

Effects of copper and butyltin compounds on the growth, photosynthetic activity and toxin production of two HAB dinoflagellates: The planktonic Alexandrium catenella and the benthic Ostreopsis cf. ovata

Controlled laboratory experiments were conducted to test the effects of copper (Cu2+) and butyltins (BuT) on the growth, photosynthetic activity and toxin content of two HABs (Harmful Algal Blooms) dinoflagellates, the planktonic Alexandrium catenella and the benthic Ostreopsis cf. ovata. Microalgae were exposed to increasing concentrations of Cu2+ (10−4 to 31 nM) or BuT (0.084 to 84 nM) for seven days. When considering the growth, EC50 values were 0.16 (±0.09) nM and 0.03 (±0.02) nM of Cu2+ for A. catenella and O. cf. ovata, respectively. Regarding BuT, EC50 was 14.2 (±6) nM for O. cf. ovata, while A. catenella growth inhibition appeared at BuT concentrations ≥27 nM. Photosynthetic activity of the studied dinoflagellates decreased with increasing Cu and BuT concentrations. For O. cf. ovata, the response of this physiological parameter to contamination was less sensitive than the biomass. Cu exposure induced the formation of temporary cysts in both organisms that could resist adverse conditions. The ovatoxin-a and -b concentrations in O. cf. ovata cells increased significantly in the presence of Cu. Altogether, the results suggest a better tolerance of the planktonic A. catenella to Cu and BuT. This could result in a differentiated selection pressure exerted by these metals on phytoplankton species in highly polluted waters. The over-production of toxins in response to Cu stress could pose supplementary health and socio-economic threats in the contaminated marine ecosystems where HABs develop.

Organotins and new antifouling biocides in water and sediments from three Korean Special Management Sea Areas following ten years of tributyltin regulation: Contamination profiles and risk assessment

A simultaneous monitoring study on organotins (butyltins and phenyltins) and most frequently used alternative antifouling biocides (Irgarol 1051, Diuron, Sea-Nine 211 and M1) in water and sediments (n=44) collected from three Special Management Sea Areas operated by Korean government. The lower concentration of butyltins (BTs) than that of new antifouling biocides (NEW) was found in water but the significant greater concentration of BTs than that of NEW was still found in sediments. The tributyltin (TBT) levels in water exceeded the chronic criterion to protect seawater aquatic life at several sites. Even ten years after the ban of the use of TBT-based antifouling paint, the concentrations of TBT, Diuron and Irgarol 1051 in sediments from shipyards exceeded global sediment quality guidelines and potentially poses adverse risks on marine organisms and extremely high concentration of TBT up to 2304ng/g was found for a sediment collected at a shipyard.

Spatiotemporal distributions of butyltin compounds in various intertidal organisms along the Samcheok and Tongyeong coasts of Korea

Thirteen years ago, the Korean Government introduced a regulation prohibiting the use of tributyltin (TBT), which was a component of antifouling paints. A subsequent decline in the concentration of butyltins (BTs) was recorded in seawater and the sediment, however, the current concentration of BTs in biota has not been well documented. The spatiotemporal distribution and concentration of BTs was recorded in biota from 2013 to 2015 along the coasts of Samcheok and Tongyeong using GS/MSD analysis. Crustaceans contained the greatest concentrations of BTs, followed by gastropods, fishes, and bivalves. We found that the concentration of BTs was greater at Tongyeong compared to Samcheok, because of the geographical characteristics of the area. We also confirmed that the regulation has been effective by showing that the TBT concentration decreased over the 3-year study period. The TBT levels of gastropods and bivalves fell within the limits of the guidelines and/or the effective concentration of the toxicological endpoint reported previously. The concentration of BTs also varied among species, being dependent on the weight of the soft tissue. Furthermore, the greater quantities of BTs degradation products compared to TBT confirmed the absence of recent inputs of pollutants during the study periods. However, compared with other Asian countries, biota BTs were greater in Korea, with noticeably greater concentrations along the south coast. Thus, further investigation of the distribution of BTs along the Korean coasts is required in the future. In conclusion, our results provide useful information about the recent trends of BTs in Korea.

Tributyltin and its Derivative in Water Samples of National Inland Water Way Authority Harbour of Warri, Delta State, Nigeria

Surface water samples were collected and analyzed to evaluate the fate of tributyltin (TBT) and its derivatives dibutyltin (DBT) and monobutyltin (MBT) from National Inland Waterway Authority (NIWA) Harbour, using gas chromatography coupled with flame ionization detection (GC-FID) with detection limit of 0.001 μg/l. The concentrations were in the range of TBT (0.01 μg/l to 0.05 μg/l), DBT (0.01 μg/l to 0.03 μg/l) and MBT (0.01 μg/l to 0.02 μg/l). The total butyltin concentration ranged from 0.04 μg/l to 0.09 μg/l. TBT was generally dominant in most of the samples, suggesting fresh inputs of tributyltin compounds and/or less degradation of TBT. The measured mean concentrations in surface water samples exceeded the ecotoxicological benchmark of 0.01 μg/l recommended by US Environmental Protection Agency (USEPA) indicative of potential environmental risk. This survey provides baseline data on tributyltin compound contamination in National Inland Waterway Authority (NIWA) Harbour and suggests further environmental monitoring of other Nigeria harbours.

Occurrence and removal of butyltin compounds in a waste stabilisation pond of a domestic waste water treatment plant of a rural French town.

The aim of this study was to investigate the fate and behaviour of butyltin pollutants, including monobutyltin (MBT), dibutylin (DBT), and tributyltin (TBT), in waste stabilisation ponds (WSP). The study was conducted as part of a baseline survey and included five sampling campaigns comprising bottom sludge and the water column from each pond from a typical WSP in France. Butyltins were detected in all raw wastewater and effluents, reflecting their widespread use. Our results revealed high affinity between butyltins and particulate matter and high accumulation of butyltins in the sludge taken from anaerobic ponds. The dissolved butyltins in the influent ranged from 21.5 to 28.1 ng(Sn).L(-1) and in the effluent, from 8.8 to 29.3 ng(Sn).L(-1). The butyltin concentrations in the sludge ranged from 45.1 to 164 and 3.6-8.1 ng(Sn).g(-1) respectively in the first and last ponds. Our results showed an average treatment efficiency of 71% for MBT, 47% for DBT, 55% for TBT. Laboratory sorption experiments enabled the calculation of a distribution coefficient (Kd = 75,000 L.kg-1) between TBT and particulate matter from the WSPs. The Kd explained the accumulation and persistence of the TBT in the sludge after settling of particulate matter. The continuous supply of contaminated raw wastewater and the sorption-desorption processes in the ponds led to incomplete bio- and photolytic degradation and to the persistence of butyltins in dissolved and particulate matrices throughout the survey period. It is thus recommended to use shallow ponds and to pay particular attention when sludge is used for soil amendment.

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.

The effect of size and epibiotic barnacles on imposex in Stramonita haemastoma collected from the northern coast of Tunisia

Imposex was quantified in Stramonita haemastoma from the Bizerta Channel during a one-year study period and the effect of gastropod size and shell fouling by epibiotic barnacles investigated. Butyltin concentrations (tributyltin (TBT) and its derivatives di- and mono-butyltin) were also investigated in the soft tissue of the gastropods to depict temporal trends in pollution. Kelibia Beach was chosen as a reference site (not polluted by organotin) to depict whether barnacle fouling could intervene in imposex development. Imposex incidence in the Bizerta Channel was greater in females fouled by epibiotic barnacles compared to non-fouled females. Considering the size of the gastropods, large females (fouled and non-fouled) always exhibit higher imposex indices than smaller females. The concentrations of organotin compounds were found to be similar in the studied species, independent of sex or fouling condition. For Kelibia Beach, no imposex was recorded in fouled and non-fouled snails, while butyltins were below the limit of detection. Results gathered in the present study confirm the effect of size and epibiotic barnacles as factors affecting imposex quantification in gastropods. The absence of imposex for Kelibia Beach suggests that barnacles do not promote the development of imposex, but could be a secondary factor amplifying the effect of imposex. Furthermore, this investigation showed a significant decrease in imposex and TBT levels in the Bizerta Channel as compared to previous work, reflecting the effectiveness of a TBT ban on a global scale.

A combined whelk watch suggests repeated TBT desorption pulses

Environmental quality in coastal Europe has improved since the complete 2003 ban on the use of tributyltin (TBT) in antifouling paints. However, there is evidence that TBT is entering the water column, presumably from illegal practices. We determined the concentration of butyltins (BTs: TBT and derivatives) in populations of two gastropods, the rock snail Nucella lapillus (n=17) and the mud snail Nassarius reticulatus (n=18) at regular intervals from pre-ban times until 2009 and 2011, respectively, in NW Spain. Although a substantial decline in TBT occurred shortly after the ban, no significant changes were observed in either species over the last 3-year period of study. In addition, the proportion of TBT relative to the sum of BTs (a marker of recent pollution) in the most recent rock snail samples unexpectedly increased; this proportion therefore showed a generally decreasing but oscillatory trend over time. The results are consistent with the theoretical expectation of BT desorption from sediments; however, this natural phenomenon is now interpreted as a recurrent episode rather than a unique, transient event. Evidence of this subtle input improves our understanding of TBT persistence in the environment in Europe and worldwide.

Composition and source of butyltins in sediments of Kaohsiung Harbor, Taiwan

Fifty-eight sediment samples were collected from the Kaohsiung Harbor (Taiwan) for analyses of monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT), using gas chromatography/flame photometric detector (GC/FPD). The concentration of total butyltins (ΣBTs), sum of MBT, DBT, and TBT, varied from 3.9 to 158.5 ng Sn/g dw in sediment samples with TBT being the major component of the sediment samples, except for the vicinity of the Love River mouth where MBT was the most abundant BT compound (a proportion of over 57%). Based on the BTs concentration, distribution, composition and correlations, the sources of BTs found in harbor sediments are shipping activities, and TBT is the main pollutant; the estuary (i.e. Love River) has been the anthropogenic source of MBT from upstream inputs. Influences of TBT on aquatic organisms are evaluated using the toxicity guidelines proposed by the US EPA (US Environmental Protection Agency) and the ACCI (assessment class criterion for imposex) proposed by OSPAR (Oslo and Paris Commission). The evaluation shows that the TBT contained in the sediment at Kaohsiung Harbor is likely to have a negative influence at ACCI class C because gastropods present imposex and TBT levels are above ecotoxicological assessment criteria (EAC) limits.