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.

Fit-for-Purpose Assessment of QuEChERS LC-MS/MS Methods for Environmental Monitoring of Organotin Compounds in the Bottom Sediments of the Odra River Estuary.

Organotin compounds (OTCs) are among the most hazardous substances found in the marine environment and can be determined by either the ISO 23161 method based on extraction with non-polar organic solvents and gas chromatography analysis or by the recently developed QuEChERS method coupled to liquid chromatography-mass spectrometry (LC-MS/MS). To date, the QuEChERS LC/MS and ISO 23161 methods have not been compared in terms of their fit-for-purpose and reliability in the determination of OTCs in bottom sediments. In the case of ISO 23161, due to a large number of interferences gas chromatography-mass spectrometry was not suitable for the determination of OTCs contrary to more selective determination by gas chromatography with an atomic emission detector. Moreover, it has been found that the derivatization of OTCs to volatile compounds, which required prior gas chromatography determination, was strongly affected by the sediments' matrices. As a result, a large amount of reagent was needed for the complete derivatization of the compounds. Contrary to ISO 23161, the QuEChERS LC-MS/MS method did not require the derivatization of OTC and is less prone to interferences. Highly volatile and toxic solvents were not used in the QuEChERS LC-MS/MS method. This makes the method more environmentally friendly according to the principles of green analytical chemistry. QuEChERS LC-MS/MS is suitable for fast and reliable environmental monitoring of OTCs in bottom sediments from the Odra River estuary. However, determination of di- and monobutyltin by the QuEChERS LC-MS/MS method was not possible due to the constraints of the chromatographic system. Hence, further development of this method is needed for monitoring di- and monobutyltin in bottom sediments.

Simultaneous analysis of butyltins and total tin in sediments as a tool for the assessment of tributyltin behaviour, long-term persistence and historical contamination in the coastal environment.

This study presents a new approach for the investigation of tributyltin (TBT) behaviour and fate in the marine environment. The approach is based on a simultaneous analysis of butyltins (BuTs) and total Sn in sediments, thus enabling an assessment of long-term persistence and historical input of TBT. The study also presents first evaluation of the extent to which the TBT-antifouling paints contribute to the contamination of coastal environments with inorganic Sn; it was demonstrated that the inorganic Sn in the investigated areas primarily originates from TBT degradation. The study was conducted by analyzing BuTs and total Sn in sediments from 34 locations along the Croatian Adriatic coast. The results revealed that 85% of the locations were contaminated with both BuTs and inorganic Sn. The share of Æ©BuTs/total Sn was low (<10%) even in sediments with low TBT degradation efficiency (TBT/Æ©BuTs >40%), demonstrating that only small portion of TBT introduced into the water column reached the sediment before being degraded. This means that recent TBT input into the marine environment may be at least 10 times higher than the amount estimated if only BuTs levels in sediments are considered. It was also demonstrated that TBT concentration in sediments with TOC <1% is not a good indicator of the overall pollution level, even if TBT/TOC approach is used in pollution assessment. Finally, in situ investigation showed that resuspension of contaminated sediments leads to significant release of MBT and DBT into the water column, whereas TBT mainly remains in sediment.

Unusual tin organics, DDX and PAHs as specific pollutants from dockyard work in an industrialized port area in China.

In order to recognize organic contaminants responsible for ecological stresses from intensive shipping traffic and dockyard works, this study aimed at characterizing the sediment contamination of a large industrialized port located in Hainan Island, China. Surface sediment samples were collected from 17 stations including the main docks, the dockyards and the major industrial wastewater outlets. Organotin compounds, the pesticide DDT (bis(chlorophenyl)trichloroethane) and its metabolites and polycyclic aromatic compounds were identified as main pollutant groups by GC/MS applying a non-target screening approach. The pesticide DDT and its metabolites were found in the same samples as the organotin derivatives pointing to similar emission sources. The concurrent presence of these compounds in the dockyard samples suggests a combined usage of organotin compounds and DDT as active ingredients in antifouling paints in Yangpu. As highly specific molecular indicators for dockyard activities, butyltin and phenyltin compounds were identified. Noteworthy, also tributylmethyltin and triphenylmethyltin were detected, likely resulting from microbial assisted biomethylation of synthetic organotin compounds in the sediments. The concentrations of PAHs, DDX and TBT in sediments from dockyards exceeded global sediment quality guidelines and the toxicity thresholds, and potentially have adverse biological effects on marine organisms.

Coupled Application of Antioxidant Defense Response and Embryo Development in Amphipod Crustaceans in the Assessment of Sediment Toxicity.

Survival rate, frequency of malformed embryos, and antioxidant defense system responses in the benthic amphipod Gmelinoides fasciatus from the Baltic Sea were measured to examine the effects of toxic sediments, and to assess the usefulness of these endpoints in sediment toxicity biotesting. A highly contaminated sediment sample from the Baltic Sea was diluted with sediment from a clean site to come up with a series of 5 test sediments with dilutions from 1:32 to 1:1024, and the reference sediment. The 1:32 dilution of the test sediment was analyzed for organotins (2862 µg tin [Sn] kg dry wt -1 ), polycyclic aromatic hydrocarbons (6064 µg kg dry wt -1 ), and selected trace metals (e.g., copper 352 mg kg dry wt -1 ). The survival rate of G. fasciatus (10-d toxicity test) was 100% in the reference and 1:1024 treatments, and began to decline from the 1:256 dilution onward. In a 28-d experiment, various types of morphological malformations were observed in 11 to 80% of the amphipod embryos in the 1:64, 1:128, and 1:256 dilutions, with only <5% in the reference treatment. Also, elevated activities in the antioxidant defense system enzymes glutathione S-transferase and catalase were observed in amphipods exposed to the contaminated sediments compared with the reference treatment, with responses at lower contamination levels compared with the appearance of malformations in the embryos. The results obtained illustrate the effectiveness of the combined application of embryonic malformations and antioxidant defense system biomarkers in amphipods in the assessment of sediment toxicity, and potentially also of sublethal effects of chemical contamination in aquatic ecosystems. Environ Toxicol Chem 2019;38:2020-2031. © 2019 SETAC.

Assessment of the organotin pollution in the coastal sediments of the Western Arabian Gulf, Saudi Arabia.

Organotin compounds (OTCs) are persistent pollutants and are considered as chemicals of environmental concern. They enter the marine environment from the antifouling paints containing organotin compounds on the hulls of ships and boats. We report the results of a study conducted in 2015 on the level of butyltins (TBT, DBT, and MBT) and phenyltins (TPhT, DPhT, and MPhT) in the sediments collected from three fishing harbors (Jubail, Khobar, and Qatif) and a reference site (Half Moon Bay). The concentrations of OTCs in the sediments vary widely among the different sampling locations. Overall, the phenyltins contribute more than the butyltins and the order of the abundance is: MPhT > DPhT > MBT > DBT > TPhT. In most stations, the concentrations of MBT are higher than DBT. The sediments from Khobar and Qatif are moderately polluted, whereas those from the Jubail are ranked as highly polluted. The concentrations of TBT at all study sites are less than the detection limit, and hence, the environmental and ecotoxicological risks are low.

Ballast water management system: Assessment of chemical quality status of several ports in Adriatic Sea.

Oxidant treatment of ballast water (BW) is commonly used in BW systems in order to minimize the transport of alien species. The release of disinfection by-products (DBPs) associated to the treatment of BW and cross-contamination of butyltin (BT) compounds through BW discharge is a topic of environmental concern. A chemical port baseline survey has been conducted in seven ports of the Adriatic Sea. Analysis have been performed on transplanted mussels, surface sediment, seawater, BW. Results showed an evidence of BT contamination, particularly in sediments, probably related to their illegal usage or to intensive shipping activities. Therefore, BW may act as a vector and contribute to re-buildup of BT contamination in the coastal regions. A baseline set of data concerning DBPs is provided, showing the preferential distribution of these compounds in the marine environment that will be useful for future considerations on monitoring and assessment of chemical contamination associated with BW.

Meiofaunal communities in four Adriatic ports: Baseline data for risk assessment in ballast water management.

Ports receive a variety of contaminants related to a wide range of anthropogenic activities - including ship ballast water (BW) - that ultimately find their way to sediments. Benthic meiofauna from four Adriatic ports (Ancona, Trieste, Koper, and Split) was assessed for the main environmental pollutants, to evaluate the effects of human activities on meiobenthos and identify the most appropriate descriptor to assess the ecological quality of marine ecosystems. Sediment analysis demonstrated that Trieste and Split were the most contaminated ports, followed by Koper and Ancona. All meiofaunal parameters showed high spatial and temporal variability, in line with the marked heterogeneity of the four ports. Sand, total organic carbon, and pollutants seemed to be the variables that best explained meiofaunal patterns. Community structure and rare taxa were the meiofaunal descriptors that reflected the environmental status and biological response most accurately. The present data suggest that meiofauna can be used to assess the biological impact of BW.

Occurrence and health risk assessment of organotins in waterworks and the source water of the Three Gorges Reservoir Region, China.

The occurrence and health risks of organotins (OTs) in the waterworks and source water in the Three Gorges Reservoir Region (TGRR), China were assessed in this study. Water samples were collected at four waterworks (A, B, C, and D) in March and July 2012 to analyze butyltins (BTs) and phenyltins (PTs) using a gas chromatography-mass spectrometry (GC-MS) system. Our results showed that both the waterworks and their nearby water sources were polluted by OTs, with PTs being the most dominant species. Monobutyltin (MBT), monophenyltin (MPT), diphenyltin (DPT), and triphenyltin (TPT) were detected in most of the analyzed water samples. The highest concentrations of OTs in influents, effluents, and source water in March were 52.81, 17.93, and 55.32 ng Sn L-1, respectively. Furthermore, significant seasonal changes in OTs pollution were observed in all samples, showing pollution worse in spring compared with summer. The removal of OTs by the conventional treatment processes was not stable among the waterworks. The removal efficiency of OTs in July reached 100% at plant B, while that at plant C was only 38.8%. The source water and influents shared similar composition profiles, concentrations, and seasonal change of OTs, which indicated that OTs in the waterworks were derived from the source water. A health risk assessment indicated that the presence of OTs in the waterworks would not pose a significant health risk to the population, yet their presence should not be ignored.

Assessment of organotins and imposex in two estuaries of the northeastern Brazilian coast.

Butyltin compounds (BTs) were used worldwide, especially because of their properties as biocides. Due to its high toxicity, the use of tributyltin (TBT) in antifouling paints has been prohibited in most countries. The occurrence and impact of BTs were assessed in surface sediments and in Stramonita rustica populations of two tropical estuaries that host major ports in northeastern Brazil. ΣBT concentrations ranged from

Binary mixture toxicities of triphenyltin with tributyltin or copper to five marine organisms: Implications on environmental risk assessment.

Triphenyltin (TPT) often coexists with tributyltin (TBT) and Cu in coastal waters worldwide. The combined toxic effect of TPT and TBT has always been assumed to be additive without any scientific proof, and the combined effect of Cu and TPT on marine organisms has not been vigorously studied. This study, therefore, investigated the acute toxicity of binary mixture of TPT/Cu and TPT/TBT to five selected marine species including Thalassiosira pseudonana, Skeletonema costatum, Tigriopus japonicus, Brachionus koreanus and Oryzias melastigma. The interaction between TPT and TBT or Cu was modeled antagonistic based on concentration addition (CA) model, while it was synergistic according to response addition (RA) model. Both model well predicted the toxicity of binary mixtures to the five organisms. As for the environmental risk assessment, CA overestimated the toxicity in most cases and thus is a more conservative model than RA model for assessing the toxicity of these chemical mixtures.

Spatiotemporal distribution and risk assessment of organotins in the surface water of the Three Gorges Reservoir Region, China.

The water quality security of the Three Gorges Reservoir during different operating periods has been a subject of recent concern. This study is the first to report the spatiotemporal variability of organotins (OTs) in surface water under dynamic water level conditions in the Three Gorges Reservoir Region (TGRR). TGRR surface water was collected during three monitoring campaigns to analyze butyltins (BTs) and phenyltins (PTs) using a gas chromatography-mass spectrometry system. Our results showed that TGRR surface water was polluted by BTs and PTs, with mono-OTs being the dominant species. A wide range of BTs and PTs concentrations was observed across the study area, but tributyltin (TBT) displayed extensive spatial distribution, and the highest concentrations consistently occurred in the downstream region of the TGRR study area, with a maximum of 393.35 ng Sn/L in Zigui (S27). The total OTs contamination level decreased over time. The diphenyltin concentration exhibited significant seasonal variation, while other OTs showed seasonal changes only during two monitoring campaigns, with the exception of dibutyltin. An ecological risk assessment indicated that both TBT and triphenyltin posed risks to aquatic organisms in TGRR surface water. We urgently recommend continuous monitoring and further measures to prevent and control OTs pollution in the TGRR.

Health risk assessment of the intake of butyltin and phenyltin compounds from fish and seafood in Taiwanese population.

Organotin compounds have been applied as stabilizers for PVCs, fungicides, and pesticides, those can enter water systems through antifouling paints on ships as well as from diverse industrial and agricultural processes. This study aims to monitor the background levels of six organotins in 200 fishery products. In the current study, the high organotin levels are over tolerable average residue levels in Taiwan. Phenyltins (PTs) levels in fish and seafood are higher than butyltins (BTs). Risk assessment showed that 95% upper confidence limits of the hazard index (HI) of organotins were almost all over 1, indicating that there are probability of health impacts for organotin consumption in Taiwanese consumers. Those who consume higher amounts of seafood and fishery may be at a higher risk of health issues, but the data indicate that organotin levels have become controlled in recent years as compared with health risk data published in 2006.

Distribution of butyltin compounds in Brazil's southern and southeastern estuarine ecosystems: assessment of spatial scale and compartments.

Butyltin compounds (BTs), including tributyltin (TBT) and its degradation products, dibutyltin and monobutyltin, have been found in a diversity of aquatic systems and causing toxic effects in target and nontarget organisms. They enter in coastal systems through different sources (as antifouling paints, industrial effluents, etc.) where they interact with biotic and abiotic components, and their distribution is commonly determined by the morphological and hydrodynamic conditions of the coastal systems. In this study, we discuss the contamination by BTs on a spatial scale (eight estuaries with three subareas each) and in different compartments of the estuaries (sediments, suspended particulate matter (SPM), and estuarine catfish tissues (liver and gills). Lower concentrations of BTs were found in the sediments (n.d. to 338 ng g(-1)) in comparison to studies before a ban of TBT in antifouling paints was enacted, mostly indicating an old input or preservation related with sediment properties and composition. For SPM samples (n.d. to 175 ng L(-1)) as well as in fish tissues (n.d. to 1426 ng g(-1)), the presence of these compounds was frequent, especially in the fish due to their movement throughout the estuaries and the potential to assess point sources of BTs. These results indicate that BTs persist in the environment, with variation in amounts between investigated estuaries and even at locations inside the same estuary, because of ideal preservation conditions, transport to remote areas, and input from different sources.

Assessment of background concentrations of organometallic compounds (methylmercury, ethyllead and butyl- and phenyltin) in French aquatic environments.

The aim of this work is to estimate background concentrations of organometallic compounds, such as tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPhT), diphenyltin (DPhT), monophenyltin (MPhT), methylmercury (MeHg), inorganic mercury (iHg) and diethyllead (Et2Pb) in the aquatic environment at the French national scale. Both water and sediment samples were collected all over the country, resulting in 152 water samples and 123 sediment samples collected at 181 sampling points. Three types of surface water bodies were investigated: rivers (140 sites), lakes (19 sites) and coastal water (42 sites), spread along the 11 French river basins. The choice of sites was made on the basis of previous investigation results and the following target criteria: reference, urban sites, agricultural and industrial areas. The analytical method was properly validated for both matrices prior to analysis, resulting in low limits of quantification (LOQ), good precision and linearity in agreement with the Water Framework Directive demands. The results were first evaluated as a function of their river basins, type of surrounding pressure and water bodies. Later, background concentrations at the French national scale were established for both water and sediment matrices, as well as their threshold, i.e., the concentration that distinguishes background from anomalies or contaminations. Background concentrations in water are ranging between <0.04-0.14 ng Hg. L(-1) for MeHg, <0.14-2.10 ng Hg. L(-1) for iHg, <1.0-8.43 ng Pb. L(-1) for Et2Pb and 0.49-151 ng Sn. L(-1), <0.08-3.04 ng Sn. L(-1) and <0.08-0.25 ng Sn. L(-1) for MBT, DBT and TBT, respectively. For sediments, background concentrations were set as <0.09-1.11 ng Hg. g(-1) for MeHg, <0.06-24.3 ng Pb. g(-1) for Et2Pb and <1.4-13.4 ng Sn. g(-1), <0.82-8.54 ng Sn. g(-1), <0.25-1.16 ng Sn. g(-1) and <0.08-0.61 ng Sn. g(-1) for MBT, DBT, TBT and DPhT, respectively. TBT occurs in higher concentrations than the available environmental protection values in 24 and 38 sampling sites for both water and sediment samples, respectively. Other phenyltins (MPhT and TPhT) did not occur above their LOQ and therefore no background was possible to establish. Throughout this work, which is the first assessment of background concentrations for organometallic compounds at the French national level ever being published, it was possible to conclude that over the last 10-20 years organotin concentrations in French river basins have decreased while MeHg concentration remained stable.

Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area.

Twelve organotins (methyl-, octyl-, butyl-, and phenyl-tin), and eight tin-free antifouling paints and their degradation products were measured in marine sediments from the Korean coastal area, and Busan and Ulsan bays, the largest harbor area in Korea. The total concentration of tin-free antifouling paints was two- to threefold higher than the total concentration of organotins. Principal component analysis was used to identify sites with relatively high levels of contamination in the inner bay area of Busan and Ulsan bays, which were separated from the coastal area. In Busan and Ulsan bays, chlorothalonil and DMSA were more dominant than in the coastal area. However, Sea-Nine 211 and total diurons, including their degradation products, were generally dominant in the Korean coastal area. The concentrations of tin and tin-free compounds were significantly different between the east and west coasts.

The occurrence of organic contaminants in European eel (Anguilla anguilla) in Poland: an environmental quality assessment.

The objective of the present study was to provide information on the levels of pollutants in the tissues of eels caught in Polish waters. The contaminants included in the study are those which have not yet been widely studied in eel stocks, but which arouse concern in relation to the environment. An overview of the pollutant levels in eels caught in other European waters was also conducted. The results are evaluated in terms of environmental quality and consumer health. The mean concentrations of ΣPBDEs and ΣHBCDs in muscles of eels sampled in Polish waters were between 1 and 2 ng g(-1) ww. The mean TBT concentrations were between 2 and 4 ng g(-1)ww with the exception of samples from the Szczecin Lagoon, in which the mean TBT concentration was about tenfold higher.

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.

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

A fugacity-based model was developed to simulate the bioaccumulation of butyltins in the food web of the Jincheng Bay mariculture area. The predicted biological tissue residues of tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) were 0.04-17.09, 0.14-53.54, and 0.27-108.77 ng-Sn g(-1), respectively, and the predicted values in six mollusca agreed well with the measured ones. The lipid-normalized concentrations did not significantly increase across trophic levels, indicating no biomagnification across aquatic food webs. These results were highly consistent with those observed both in the laboratory and field, which had been reported in numerous references. The explanation, from calculating their flux equilibrium in the food web, was that butyltins were primarily taken in via respiration from the water column by marine organisms. The sensitivities of the model parameters were analyzed, revealing that the hydrophobicity of butyltins played the dominant role in their bioaccumulation phenomena. The verified model predictions of the biotic tissue concentrations of the butyltins could be readily applied to perform internal ecological risk and human health risk assessments in this area.

A temporal and spatial assessment of TBT concentrations at dredged material disposal sites around the coast of England and Wales.

Despite legislative interventions since the 1980s, contemporary concentrations of organotin compounds in marine sediments still impose restrictions on the disposal of dredged material in the UK. Here, we analyse temporal and spatial data to assess the effectiveness of the ban on the use of TBT paints in reducing concentrations at disposal sites. At a national scale, there was a statistically significant increase in the proportion of samples in which the concentration was below the limit of detection (LOD) from 1998 to 2010. This was observed for sediments both inside and outside the disposal sites. However, this temporal decline in organotin concentration is disposal site-specific. Of the four sites studied in detail, two displayed significant increases in proportion of samples below LOD over time. We argue that site-specificity in the effectiveness of the TBT ban results from variations in historical practices at source and unique environmental characteristics of each site.