An alternative silicone-based passive sampling device to derive organotin concentrations in the aqueous phase.

Organotin compounds (OTs) are well studied in various environmental compartments, with a critical focus on the water column as their primary entry point into aquatic ecosystems. In this context, a method for the analysis of organotin (OTs) in water using silicone rubber-based passive sampling was optimized, validated, and field-tested. Validation covered crucial parameters, including the limit of detection (LOD), limit of quantification (LOQ), accuracy, precision, linearity, and matrix effect. The method was shown to be robust (R2 ≥ 0.99), with recoveries between 70.2 and 114.6%, and precise (CV < 12.8%) (N = 3). LODCw and LOQCw were ≤15 and ≤ 48 pg Sn L-1, respectively, for TBT and TPhT. The matrix effect showed to be low (>-20% ME < 20%) for all OTs but TPhT (69.4%). The silicone rubber-water partition coefficients (Log Ksr,w) were estimated at 3.37 for MBT, 3.77 for DBT, 4.17 for TBT, 3.49 for MPhT, 3.83 for DPhT, and 4.22 for TPhT. During the field study carried out between October 2021 and February 2022 at the entrance of the Port of Santos navigation channel (Southeastern Brazil), sampling rates ranged between 4.1 and 4.6 L d-1, and the equilibrium was achieved for MBT, DBT, MPhT, and DPhT after ∼45 days of deployment. The freely dissolved concentrations varied between 134 and 165 pg Sn L-1 for TBT, 388 and 610 pg Sn L-1 for DBT, and 1114 and 1509 pg Sn L-1 for MBT, while MPhT, DPhT, and TPhT were below the limit of detection. Results pointed out that J-FLEX® rubber-based passive sampling is a suitable and reliable alternative method for the continuous monitoring of OTs in the water column.

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.

Occupational exposure to organotin substances: Development of a liquid chromatographic separation method for 11 organotin compounds in workplace air samples via HPLC-ICP-MS.

Organotin compounds (OTCs) are widely regulated but rank among the most used organometallic compounds in various industrial sectors. They are significantly more toxic than inorganic tin compounds. At workplaces, OTCs can be released as vapors or dust particles and can be absorbed by inhalation or skin contact. Occupational exposure thus represents a great risk for the absorption of OTCs for employees. Methods for OTCs speciation in workplace air monitoring currently do not exist. This study describes the development of a separation method for eleven in Germany regulated OTCs via HPLC-ICP-MS. The method allows a near baseline separation of MMT, MBT, MOT, MPhT, DMT, DBT, DPhT, TMT, TBT, TPhT and TTMT within 22 min on a C18 column and a ternary solvent and flow rate gradient using methanol, acetonitrile, and ultrapure water + 6% (v/v) acetic acid + 0.17% (m/v) α-tropolone. Ten analytes show linearity in the working range of 10 - 100 µg OTCs/L with R² > 0.999. Due to its high volatility the analyte TTMT showed a quadratic relationship between concentration and signal intensity with R² = 0.9998. The determination of the instrumental limits resulted in detection limits between 0.14 and 0.57 µg Sn/L and limits of quantification between 0.49 and 1.97 µg Sn/L. Over the course of this study thermal instability and cross reactivity of OTC in solution became apparent. Formation of two reaction products in mixed OTCs solutions have been observed. These effects will further be examined within development of appropriate sampling and sample preparation for workplace air to provide a suitable method for the determination of OTCs at workplaces according to normative references.

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.

Organotin compounds in seafood by ultrasonic assisted extraction and gas chromatography-triple quadrupole tandem mass spectrometry.

Although restricting environmental quality values for organotin compounds (OTs) are set by Directive 2013/39/EU of the European Parliament, marine environment remains being affected due to maritime circulation at global scale. Fish and seafood accumulate OTs, making fish and seafood consumption the main source of OTs in humans. Because of the fish and seafood matrices complexity and the required low limits of detection, a robust and fast procedure for the quantification of OTs in fish and seafood, using ultrasound-assisted extraction and gas chromatography-tandem mass spectrometry, was validated and applied. Detection (2.7 µg Sn kg-1) and quantification (8.0 µg Sn kg-1) limits, repeatability and intermediate precision (<10%), accuracy by analysing ERM®-CE477 Mussel Tissue and analytical recoveries (65-122%) were assessed. Multivariate analysis shown that the matrix effect for some OTs displayed good negative correlation with the fat and protein content. Health risk assessment of OTs intake revealed no serious risk for human consumption.

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.

Organotins Remain a Serious Threat to the Indo-Pacific Humpback Dolphins in the Pearl River Estuary.

Marine mammals often accumulate high levels of environmental contaminants, even those that are globally regulated regarding usage, raising concerns about their health status. Here, we conducted the first investigation of tissue distribution, spatiotemporal trends, and potential risks of six organotin compounds (OTs) in Indo-Pacific humpback dolphins (n = 101) from the northern South China Sea during 2003-2021. We detected the highest level of hepatic triphenyltin in these humpback dolphins compared with the results reported in cetaceans globally, and the liver accumulated the highest OT concentrations than other analyzed tissues. Despite the downward trend of butyltins in humpback dolphins after the global ban on the use of OTs as antifouling paints, levels of phenyltins have continued to increase over the past 20 years, suggesting that the other applications of phenyltins in South China remain prevalent. In vitro and in vivo analyses revealed that tissue-relevant doses of OTs could induce agonistic effects on the dolphin peroxisome proliferator-activated receptor γ as a master regulator of lipid homeostasis and altered the dolphin fatty acid profiles. Our results highlight the lipid-disrupting effects of current OT exposure in humpback dolphins and emphasize the need for further efforts to eliminate OT contamination in South China.

Organotin contamination in seafood from the Yucatán Peninsula, Mexico: Is there a potential risk for the health of consumers?

Since seafood is considered an important source of organotin compounds (OTCs), the present study assessed the potential risk to human health of ingesting butyltins (BTs) and phenyltins (PhTs) along with this type of food. Seafood samples were collected at five fishing sites in the Yucatán Peninsula (Mexico) during February and March 2018. In general, organotins were detected in all samples, suggesting a widespread occurrence of these compounds in the investigated region. The average concentration of total organotins in the muscle of demersal fish (Lutjanus synagris, Lutjanus campechanus, Calamus pennatula, Haemulon plumierii, Rhomboplites aurorubens), pelagic fish (Euthynnus alletteratus, and Opisthonema oglinum), gastropods (Melongena bispinosa and Strombus pugilis), oyster (Crassostrea virginica) and shrimp (Penaeus duorarum) was 146.7 ± 76.2, 93.1 ± 92.6, 61.0 ± 53.0, 76.7 ± 2.6, and 28.8 ± 2.7 ng Sn g-1 dry weight, respectively. Overall, MPhT among PhTs was the dominant compound in fish, while TBT among BTs was the dominant compound in shellfish. Regarding the toxic OTCs, TBT followed by DBT were the predominant compounds in all seafood species, while TPhT was below the quantification limit in most samples. The estimated daily intake values were lower than the tolerable daily intake (TDI) for the sum of organotins established by the European Food Safety Authority (EFSA). Furthermore, the hazard quotients (HQ) and hazard indices (HI) values were all lower than 1, suggesting that daily exposure to these levels of organotins is unlikely to cause any harm to the human health of seafood consumers at the Yucatán Peninsula. Thus, consumers may not be at risk through the inclusion of these investigated seafood species in their normal diet. However, due to the increasing coastal urbanization, maritime activities, and the likely illegal use of tin-based paints in Mexico, additional monitoring is needed to assess organotin levels in other regions along the Mexican coastal zone and using other seafood species.

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.

Global qualitative and quantitative distribution of micropollutants in the deep sea.

Micropollutants (MPs) include a wide range of biological disruptors that can be toxic to wildlife and humans at very low concentrations (<1 µg/L). These mainly anthropogenic pollutants have been widely detected in different areas of the planet, including the deep sea, and have impacts on marine life. Because of this potential toxicity, the global distribution, quantity, incidence, and potential impacts of deep-sea MPs were investigated in a systematic review of the literature. The results showed that MPs have reached different zones of the ocean and are more frequently reported in the Northern Hemisphere, where higher concentrations are found. MPs are also concentrated in depths up to 3000 m, where they are also more frequently studied, but also extend deeper than 10,000 m. Potentially toxic metals (PTMs), polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane (DDTs), organotins, and polycyclic aromatic hydrocarbons (PAHs) were identified as the most prevalent and widely distributed MPs at ≥200 m depth. PTMs are widely distributed in the deep sea in high concentrations; aluminum is the most prevalent up to 3000 m depth, followed by zinc and copper. PCBs, organotins, hexachlorocyclohexanes (HCHs), PAHs, and phenols were detected accumulated in both organisms and environmental samples above legislated thresholds or known toxicity levels. Our assessment indicated that the deep sea can be considered a sink for MPs.

The first observation of antifouling organotin compounds and booster biocides in sediments from Samsun Port area, Black Sea, Turkey.

The distribution of antifouling organotin compounds (OTCs) and booster biocides in surface sediments of Samsun Port (Black Sea, Turkey) in September 2014 was investigated by gas chromatography-tandem mass spectrometry (GC-MS/MS) method. The total organotin concentrations ranged from <1.0 to 669.6 ng/g, dw. Among the studied booster biocides, Diuron (<1.0-11.28 ng/g) was found in 70.58% of the investigated sediments, while Irgarol (<1.0-26.53 ng/g) was detected in two stations. Traces of fresh input organotin and high Irgarol were found at the park/repairment points of the port. The Principal Component Analysis (PCA) showed that sediment characteristic types and Total Organic Carbon (TOC) were the main relevant parameters in the accumulation of antifouling contamination in the Port area. In comparison with several types of environmental sediment quality criteria, Samsun Port is highly polluted area. The concentrations of OTCs and Diuron maybe used as a baseline reference level for future monitoring programs in Turkish Ports.

Organotin compounds (OTs) in surface sediments, bivalves and algae from the Russian coast of the Barents Sea (Kola Peninsula) and the Fram Strait (Svalbard Archipelago).

Organotin pollution in components of benthic ecosystems was investigated in 2019 in the Barents Sea (South shore, Kola Peninsula) and the Fram Strait (Icefjord, Svalbard Archipelago). Six species of organotin compounds (OTs), including monobutyltin, dibutyltin, tributyltin, tetrabutyltin, triphenyltin and tricyclohexyltin, were measured in the surface sediments, bivalve molluscs (Ciliatocardium ciliatum, Macoma calcarea, Chlamys islandica) and macrophyte algae (Saccharina latissima, Palmaria palmata, Ulvaria obscura, Fucus serratus, Fucus distichus). The results obtained showed moderate contamination of the studied samples with OTs. The total content of six tin compounds was in the ranges 35-139 ng g-1, 13-108 ng g-1 and 2.9-75 ng g-1 (dry weight) in the samples of sediments, bivalves and algae, respectively. In most cases, the concentrations of tributyltin in bottom sediments and mollusc tissues did not exceed the established international regulations. The degradation indices analysis of butyl tin derivatives indicated the active transformation of tributyltin and tetrabutyltin in bottom sediments and macrophyte algae and the accumulation of these compounds in the soft tissues of molluscs. The sediment and mollusc concentrations of OTs measured in this study were comparable to those reported for other areas of the Arctic region.

Low impact leaching agents as remediation media for organotin and metal contaminated sediments.

All over the world, elevated levels of metals and the toxic compound tributyltin (TBT) and its degradation products are found in sediments, especially close to areas associated with shipping and anthropogenic activities. Ports require regular removal of sediments. As a result, large volumes of often contaminated sediments must be managed. The aim of this study was to investigate enhanced leaching as a treatment method for organotin (TBT) and metal (Cu and Zn) contaminated marine sediments. Thus, enabling the possibility to reuse these cleaner masses e.g. in construction. In addition to using acid and alkaline leaching agents that extract the OTs and metals but reduce the management options post treatment, innovative alternatives such as EDDS, hydroxypropyl cellulose, humic acid, iron colloids, ultra-pure Milli-Q water, saponified tall oil ("soap"), and NaCl were tested. Organotin removal ranged from 36 to 75%, where the most efficient leaching agent was Milli-Q water, which was also the leaching agent achieving the highest removal rate for TBT (46%), followed by soap (34%). The TBT reduction accomplished by Milli-Q water and soap leaching enabled a change in Swedish sediment classification from the highest class to the second highest class. The highest reduction of Zn was in HPC leached samples (39% removal) and Cu in EDDS leached samples (33% removal). Although high metal and OT leaching were achieved, none of the investigated leaching agents are sufficiently effective for the removal of both metals and OTs. The results of this study indicate that leaching with ultra-clean water, such as Milli-Q water, may be sufficient to treat TBT contaminated sediments and potentially allow mass reuse.

Simultaneous Determination of Five Organotins in Tropical Fruits Using Modified QuEChERS Combined with Ultra-high Performance Liquid Chromatography-Tandem Mass Spectrometry.

A sensitive, confirmatory ultra-high performance liquid chromatography-tandem mass spectrometry based on modified QuEChERS was developed and validated to detect five organotin compounds (tributyltin chloride (TBT), triphenyltin chloride (TPT), trimethyltin chloride (TMT), azocyclotin and cyhexatin) in classical tropical fruits (mango, pineapple and banana). Fruits samples were ultrasonically extracted with methanol and subsequently purified by graphitized carbon black adsorbents. Five organotins were separated on a C18 column with the mobile phase of a mixture of methanol and 0.1% (v/v) aqueous formic acid, and detected by MS/MS under multiple reaction monitoring mode. The developed method was validated in terms of linearity, limit of detection (LOD), recovery and precision. Results were linear in their corresponding concentration ranges, with coefficients of determination (r) bigger than 0.999. The average LODs (S/N = 3) of the method for TBT, TPT, TMT, azocyclotin and cyhexatin were 1.3, 3.5, 3.2, 5.1 and 1.7 µg/kg, respectively. The average recoveries (n = 5) at three spiked levels (0.01, 0.1 and 0.2 mg/kg) ranged from 69 to 103% with relative standard deviations of 2.1-11.9%. The method is simple, effective, accurate and non-derivatized, and meets the routine monitoring requirements for trace organotins in tropical fruits.

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.

Tin and mercury and their speciation (organotin compounds and methylmercury) in worldwide red wine samples determined by ICP-MS and GC-ICP-MS.

One hundred and twenty-two red wines were analysed for their total tin, total mercury and speciation concentrations. Total Sn and Hg concentrations were in average 4.4 ± 7.2 µg/L and 0.22 ± 0.12 µg/L, respectively. Two GC-ICP-MS methods were developed and validated for speciation purposes: one to measure organotin compounds (OTCs) with internal standard correction; the other, to evaluate methylmercury (MeHg+) by isotopic dilution. Methyltins (mainly dimethyltin, but also monomethyltin) were the most abundant OTCs recovered. Methylation seems to occur biotically during the wine making process and not during the bottling time. Therefore, it also seems to be roughly dependent on the geographical origin of the wine. For higher OTCs, monobutyltin was the most regularly found, but dibutyltin and monooctyltin were also detected sometimes. MeHg+ was not recovered in any of the samples investigated, probably due to the low level of Hg. These results suggest that, in terms of these parameters, normal consumption of wine is not a hazard for human health.

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.

Ultrasensitive determination of organotin compounds in plastic food packaging and edible oils by sheathless capillary electrophoresis-electrospray ionization-mass spectrometry.

The determination of trace-amount organotins in plastic food packaging materials is of great significance in food safety. However, due to the complexity of organotins and sample treatment processes, it is still a challenging task. Here, we report a method for the sensitive and simultaneous determination of organotins in plastic food packaging materials and edible oils, by utilizing sheathless capillary electrophoresis-electrospray ionization-mass spectrometry. The method of sample pretreatment with ultrasonic extraction and solid phase extraction is used to eliminate interference. The results showed low limits of detection (LODs) of 2 pg mL-1-50 pg mL-1 and excellent inter/intra-day repeatability. Good average recoveries in the range of 80.27% to 108.52% were obtained at three spiked concentrations, with a relative standard deviation less than 8.71%. The successful simultaneous determination of the target analytes will pave the way for further assessment of contamination and migration behaviour of organotins from packaging materials to food, which is of great significance for evaluating and controlling food safety.

[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.

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.