Butyltins Research Articles

Butyl and Phenyl Tin Compounds in Fish and Shellfish on the Korean Market

The degree of organotin contamination was determined in samples of ten species of fish and shellfish that were representative of the Korean fish market. Shellfish and fish samples were collected in the fish markets of eight big cities in Korea (Gangneung, Ulsan, Pusan, Daegu, Guangju, Daejun, Incheon and Seoul). The edible portion of total 160 samples were analyzed for organotin compounds such as monobutltin (MBT), dibutyltin (DBT), tributyltin (TBT), monophenyltin (MPT), diphenyltin (DPT) and TPT (triphenyltin) by GC-MSD SIM mode after propylation and Florisil clean-up. Generally organotin levels of fish were higher than shellfish. The highest concentration of TBT was found in mackerel (average 67.02 ng/g-wet wt.) among fish and shellfish. TBT usually accounted higher percentage than that of MBT and DBT in most samples. However, the average concentration order of PTs in the tested samples was MPT > TPT > DPT except saury.

Increases in cytosolic calcium ion levels in human natural killer cells in response to butyltin exposure.

This study investigated whether exposures to butyltins (BTs), tributylin (TBT), and dibutyltin (DBT) were able to alter cytosolic calcium levels in human natural killer (NK) cells. Additionally, the effects of cytosolic calcium ion increases on the activation state of mitogen-activated protein kinases (MAPKs) in NK cells were also investigated. NK cells are an intital immune defense against the development of tumors or viral infections. TBT and DBT are widespread environmental contaminants, due to their various industrial applications. Both TBT and DBT have been shown to decrease the ability of NK cells to lyse tumor cells (lytic function). TBT has also been shown to activate MAPKs in NK cells. The results of this study indicated that TBT increased cytosolic calcium levels by as much as 100% after a 60-min exposure to 500 nM TBT, whereas DBT increased cytosolic calcium levels to a much smaller extent (and required higher concentrations). The results also indicated that increases in cytosolic calcium could activate MAPKs but only for a short period of time (5 min), whereas previous studies showed that activation of MAPKs by TBT last for at least 6 h. Thus, it appears that TBT-stimulated increases in cytosolic calcium might contribute to, but are not fully responsible for, TBT-induced activation of MAPKs.

Organotin levels in seafood from Portuguese markets and the risk for consumers

Because of their ubiquity in the aquatic environment, the antifouling agent tributyltin (TBT) and other organotins (OTs) accumulate through the food chain, resulting in the occurrence of OTs in seafood products. Despite a high number of studies on the negative impact of TBT in female prosobranch gastropods, few works exist in Europe reporting the levels of these compounds in edible parts of marine organisms used in Human diet. Therefore, within the scope of an EU project OT-SAFE the levels of several OTs were evaluated in the most relevant seafood products for Portuguese consumers. Butyltins (BTs) have been detected in all analysed groups (fish, crustaceans, bivalves, cephalopods), whereas triphenyltin, tricyclohexyltin, monooctyltin and dioctyltin could not be detected and tetrabutyltin was present above detection limits in a single sample. In general, levels of BTs in edible parts of fish, crustaceans and cephalopods collected in Portuguese markets during this study are in the lower range of that reported for these animal groups from other locations (i.e. below 30ngg−1 wet weight). In contrast, moderate to high concentrations have been observed in bivalves (up to 275ng TBTg−1 wet weight). While most samples showed TBT plus DBT levels below the tolerable average residue levels (TARL), which may indicate low risk for consumer, four bivalve samples displayed BT levels above TARL, thus indicating that higher bivalve consumer groups may be at risk. The results found are discussed in relation to the potential risk for consumers and integrated with recent finds on the molecular targets of OTs in mammals.

Intersex in Littorina littorea and DNA damage in Mytilus edulis as indicators of harbour pollution

Intersex in snails ( Littorina littorea) and DNA damage in blue mussels ( Mytilus edulis) were analysed to assess how these bio-indicators reflected the level of chemical contamination at two sites in a highly contaminated harbour in Denmark. The comet assay using mussel gill cells was an indicator of exposure to genotoxic chemicals, and the intersex index (ISI) observed in snails was an indicator of exposure to butyltin (BT) compounds. Biota and sediments were analysed for heavy metals (Cd, Cu, Pb and Zn), butyltin compounds (TBT, DBT and MBT), nine PCB congeners and 19 PAH compounds. The biological effects were found to reflect the levels of the chemicals, and it was concluded that intersex in L. littorea and DNA damage in M. edulis can be used as bio-indicators of harbour pollution.

Seasonal Variation in Organotins in the Waters of the Dona Paula Bay, West Coast of India

Surface seawaters from the Dona Paula Bay, were collected at weekly intervals during March 2007 to March 2008, and analyzed for butyltins (BT) such as tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT) using a GC-MS system. The mean concentrations of TBT, DBT, MBT and total BT varied from <1-37, 4-19, 6-28 and 21-84 ng Sn L(-1), respectively. Highest levels of BTs were recorded during May followed by April 2007 and March 2007 probably because the shipping and tourism activities are very high during these months.

Butyltin occurrence and risk assessment in the sediments of the Iberian Peninsula

The occurrence of butyltin (BT) compounds in more than 50 recent sediment samples of the Iberian Peninsula, collected in the harbours of the western Mediterranean Sea (Spain) and the North Atlantic Ocean (Portugal), including domestic and industrial sewage disposal sites, has been assessed. The highest levels of tributyltin (TBT) (7673 μg kg −1 dry wt.) were detected in commercial harbours associated with inputs from large vessels. However, relatively high TBT values (about 2150 μg kg −1 dry wt.) were also detected in fishing and recreational boating areas. Spanish marinas and harbours are more polluted in terms of TBT (5–7673 μg kg −1 dry wt.) compared to those in Portugal (4–12 μg kg −1 dry wt.). Generally, the Mediterranean sediments show a BT distribution characterized by the predominance of TBT over the degradation products dibutyl (DBT) and monobutyltin (MBT), indicating the presence of recent inputs, in contrast to the Portuguese coastal distribution. Calculation of butyltin degradation indexes (BDI) confirmed a different trend, depending on the area. Furthermore, a comparative study of the occurrence of BT in different sewage sludge disposal sites shows that domestic primary sewage sludge effluents can contribute to coastal BT pollution, but to a lesser extent when compared with harbours. Historical trends (1995–2003) for Barcelona harbour reveal that BT regulations on the use of TBT-based antifouling paints have not been fully effective. Finally, a comparison against the existing sediment quality guidelines (SQGs) indicated that acute toxic effects could only be expected for TBT in some Mediterranean harbours; conversely, in every North Atlantic Ocean station, a lesser environmental threat for the harbour benthic community is expected.

Contamination Profiles of Antifouling Biocides in Selected Coastal Regions of Malaysia

The concentrations of butyltins (BTs) in sediment from Peninsular Malaysia along the Strait of Malacca and their spatial distribution are discussed. The concentrations of BTs were high in the southern part of Peninsular Malaysia where there is a lot of ship traffic, because trade is prosperous. The concentrations of monobutyltin (MBT), dibutyltin (DBT), and tributyltin (TBT) in sediment from the coastal waters of Peninsular Malaysia were in the range 4.1-242 microg/kg dry weight (dw), 1.1-186 microg/kg dw, and 0.7-228 microg/kg dw, respectively. A higher percentage of TBT was observed in the area where TBT concentrations were high. The concentrations of monophenyltin (MPT), diphenyltin (DPT), and triphenyltin (TPT) were in the range <0.1-121 microg/kg dw, 0.4-27 microg/kg dw, and 0.1-34 microg/kg dw in sediment from Peninsular Malaysia, respectively. MPT was the dominant phenyltin species. MBT, DBT, and TBT in green mussel (Perna viridis) samples were detected in the range 41-102 microg/kg, 3-5 microg/kg, and 8-32 microg/kg, respectively. A tolerable average residue level (TARL) was estimated at 20.4 microg/kg from a tolerable daily intake (TDI) of 0.25 microg TBTO/kg body weight/day. The maximum value of TBT detected in green mussel samples was the value near the TARL. TPTs were not detected in green mussel samples. The concentrations of Diuron and Irgarol 1051 in sediment from Peninsular Malaysia were in the range <0.1-5 microg/kg dw and <0.1-14 microg/kg dw, respectively. High concentrations of these compounds were observed in locations where the concentrations of TBT were high. Sea Nine 211, Dichlofluanid, and Pyrithiones were not detected in sediment. The concentrations of antifouling biocides in Melaka and the Strait of Johor were investigated in detail. BTs were found in similar concentrations among all sampling sites from Melaka, indicating that BT contamination spread off the coast. However, Sea Nine 211, Diuron, and Irgarol 1051 in the sediment from Melaka were high at the mouth of the river. BT concentrations at the Strait of Johor were higher than those in Peninsular Malaysia and Melaka and were high at the narrowest locations with poor flushing of water. The concentrations of antifouling biocides were compared among Malaysia, Thailand, and Vietnam. A higher concentration and wide variations of TBT and TPT in sediment from Malaysia were observed among these countries. The Irgarol 1051 concentrations in sediment from Malaysia were higher than those in Thailand and Vietnam.

Toxic effects of tributyltin and its metabolites on harbour seal ( Phoca vitulina) immune cells in vitro

The widespread environmental contamination, bioaccumulation and endocrine disruptor effects of butyltins (BTs) to wildlife are well documented. Although suspected, potential effects of BTs exposure on the immune system of marine mammals have been little investigated. In this study, we assessed the effects of tributyltin (TBT) and its dealkylated metabolites dibutyltin (DBT) and monobutyltin (MBT) on the immune responses of harbour seals. Peripheral blood mononuclear cells isolated from pup and adult harbour seals were exposed in vitro to varying concentrations of BTs. DBT resulted in a significant decrease at 100 and 200 nM of phagocytotic activity and reduced significantly phagocytic efficiency at 200 nM in adult seals. There was no effect in phagocytosis with TBT and MBT. In pups, the highest concentration (200 nM) of DBT inhibited phagocytic efficiency. A reduction of tumor-killing capacity of adult natural killer (NK) cells occurred when leukocytes were incubated in vitro with 50 nM DBT and 200 nM TBT for 24 h. In adult seals, T-lymphocyte proliferation was significantly suppressed when the cells were exposed to 200 nM TBT and 100 nM DBT. In pups, the proliferative response increased after an exposure to 100 nM TBT and 50 nM DBT, but decreased with 200 nM TBT and 100 nM DBT. The immune functions were more affected by BTs exposure in adults than in pups, suggesting that other unsuspected mechanisms could trigger immune parameters in pups. The toxic potential of BTs followed the order of DBT > TBT > MBT. BT concentrations of harbour seal pups from the St. Lawrence Estuary (Bic National Park) ranged between 0.1–0.4 ng Sn/g wet weight (ww) and 1.2–13.4 ng Sn/g ww in blood and blubber, respectively. For these animals, DBT concentrations were consistently below the quantification limit of 0.04 ng Sn/g ww in blood and 0.2 ng Sn/g ww in blubber. Results suggest that concentrations measured in pups are considered too low to induce toxic effects to their immune system during first days of life. However, based on our in vitro results, we hypothesize that BTs, and DBT in particular, could pose a serious threat to the immune functions in free-ranging harbour seal adults.

Decreased TBT pollution and changing bioaccumulation pattern in gastropods imply butyltin desorption from sediments

Two monitoring surveys were repeated in Galicia (NW Spain): one in 2003 concerned the rocky shore gastropod Nucella lapillus (19 populations, the reference campaign in 1996), the other dealt in 2005 with the infaunal snail Nassarius reticulatus (25 sites, the previous one in 2000). Samples were subject to a standard protocol to determine the concentrations of butyltins (BTs) in tissues. Results show that pollution in most populations has considerably decreased over the last decade: for N. lapillus the mean descent ranged from 37% (for tributyltin -TBT-) to 66% (for monobutyltin -MBT-), and TBT concentrations were on average halved in N. reticulatus. However, derivatives generally increased in this latter species, to the extent that dibutyltin -DBT- in several 2005 samples exceeded the aggregate of all three BTs in 2000. As a consequence, a major change in the bioaccumulation patterns becomes evident, particularly when computing the butyltin degradation index [BDI: (DBT + MBT)/TBT]. This shift is most marked at sites where pollution has always been lowest, and it shows significant negative correlation between both gastropods. Since sources other than antifouling paints are not important in the area, it is proposed that observations are due to BT desorption from sediments through some interplay involving the different characteristics of the chemicals and the contrasting biology of the animals.

The content of butyl- and phenyltin derivatives in the sediment from the Port of Gdansk

Harbor sediments containing large deposits of organotin compounds constitute a potential threat to the marine environment. Samples of harbor sediments were collected twice in the years 2003 and 2005 from the following locations: Ziółkowskiego, Siarkowe, Wiślane, Węglowe, Chemików and Paliw Płynnych Quays. The cores of 25 cm length sliced into 2- and 5-cm segments were analyzed. After drying and homogenization, samples were split into two granulometric fractions, i.e. <2.00 and <0.063 mm. The dominant fraction in whole sediment, i.e. fraction grain diameter <2.00 mm, was sand (grain diameter 2.00–0.063 mm). However, the highest concentrations of butyltin (BT) and phenyltin (PT) compounds were found in the fine sediment fraction. The mean values of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) in the analyzed samples in the <2.00 mm fraction were 2144.9, 434.7 and 148.1 ngSn g −1 d.w., respectively, while the corresponding mean values in the <0.063 mm fraction were 6556.4, 1593.7 and 450.0 ngSn g −1 d.w. The mean concentrations of monophenyltin (MPhT) have been estimated at 29.0 and 49.9 ngSn g −1 d.w. for the <2.00 and <0.063 mm fraction sizes, respectively. The estimated content levels of diphenyltin (DPhT) and triphenyltin (TPhT) were in most cases below the detection limit of the applied method. The sediment cores collected from the locations characterized by high industrialization and intense exploitation (Wiślane, Węglowe Quays) contained the highest concentrations of BT and PT.

Aquadi-n-butyl(5-methylpyrazine-2-carboxylato)tin(IV) methanol solvate

In the monomeric title compound, [Sn(C4H9)2(C6H5N2O2)2(H2O)]·CH3OH, the Sn atom is seven-coordinate, displaying a distorted penta­gonal bipyramidal SnC2N2O3 geometry with the two C atoms in the axial sites. In the crystal structure, inter­molecular O—H⋯O hydrogen bonds link the complex and solvent mol­ecules into infinite chains.

Contamination status and accumulation profiles of organotins in sea otters ( Enhydra lutris) found dead along the coasts of California, Washington, Alaska (USA), and Kamchatka (Russia)

Organotin compounds (OTs) including mono- to tri-butyltins, -phenyltins, and -octyltins were determined in the liver of adult sea otters ( Enhydra lutris) found dead along the coasts of California, Washington, and Alaska in the USA and Kamchatka, Russia. Total concentrations of OTs in sea otters from California ranged from 34 to 4100 ng/g on a wet weight basis. The order of concentrations of OTs in sea otters was total butyltins ≫ total octyltins ≧ total phenyltins. Elevated concentrations of butyltins (BTs) were found in some otters classified under ‘infectious-disease’ mortality category. Concentrations of BTs in few of these otters were close to or above the threshold levels for adverse health effects. Total butyltin concentrations decreased significantly in the livers of California sea otters since the 1990s. Based on the concentrations of organotins in sea otters collected from 1992 to 2002, the half-lives of tributyltin and total butyltins in sea otters were estimated to be approximately three years.

Concentrations of Organotin Compounds in the Stranded Killer Whales from Rausu, Hokkaido, Japan

We measured the concentrations of butyltin (BT) and phenyltin (PT) compounds in blubber, liver, lung, and muscle of seven stranded killer whales (Orcinus orca) collected from Rausu, Hokkaido, Japan. BTs in blubber (n = 6), liver (n = 4), lung (n = 1), and muscle (n = 4) of adult whale were in the range of 37-90, 385-676, 15, and 26-53 microg kg(-1) wet weight, respectively. Concentrations of PTs in blubber, liver, lung, and muscle were <1 to 58, <1 to 14, 7 and <1 to 4 microg kg(-1) wet weight, respectively. Detected frequencies of PTs were low in all tissues. Higher percentages of monobutyltin (MBT) in blubber, lung, and muscle were observed, while the percentage of dibutyltin (DBT) was high in liver. Detected frequencies of triphenyltin (TPT) were highest among tissues. Total BT concentrations in blubber and liver of a whale calf were lower than those in adult whales. MBT and DBT in the liver of the calf were the same (42%). MBT in blubber was the dominant compound among BTs.

Accumulation of Organotin Compounds in Tissues and Organs of Dolphins from the Coasts of Thailand

The concentration of organotin (OT) in seven species of dolphin (bottlenose dolphin, finless porpoise, Indo-Pacific humpbacked dolphin, long-beaked common dolphin, Pantropical spotted dolphin, spinner dolphin, and striped dolphin), which were stranded on the coasts of Thailand, were measured. Butyltin (BT) and phenyltin (PT) compounds in tissues and organs of the dolphins were in the range of 16-1,152 microg kg(-1) and <1-62 microg kg(-1), respectively. The highest concentration of tributyltin (TBT) was generally observed in the liver. Because of the lower concentration of TPT, a trend in body distribution was not observed. Monobutyltin (MBT) among all the BTs was the dominant species in tissues and most organs except the liver. However, dibutyltin (DBT) was predominant in the liver. Monophenyltin (MPT) was not detected in all dolphins in the study. The higher concentration of BTs was observed with the increase in body length of dolphins. On the other hand, no significant difference in the concentration of OTs between genders was observed. The concentrations of OTs in tissues and organs were compared among dolphin, whales, and dugongs stranded on the coasts of Thailand. The concentrations of BTs were high and in the order of whales > dugongs > dolphins and the concentrations of PTs in whales were higher than those in dolphins and dugongs.

Headspace solid-phase micro-extraction and gas chromatography-ion trap tandem mass spectrometry method for butyltin analysis in sediments: Optimization and validation

In this work, headspace solid-phase micro-extraction (SPME) combined with gas chromatography-mass spectrometry (GC-MS) method for analysis of butyltin compounds in sediment samples was upgraded by the introduction of tandem mass spectrometry (MS/MS). Optimization and validation of this method based on an one step procedure, tetraethylborate in situ ethylation with simultaneous extraction by headspace SPME, combined with tandem mass spectrometry is described. A simple leaching/extraction step of mono-(M), di-(D) and tri-(T) butyltin (BT) compounds from the sediment is required as sample pre-treatment. The combination of the two techniques headspace SPME and MS/MS, led to very little matrix interference which permitted to attain limits of detection three or more orders of magnitude lower than those attained in previous methods: 0.3 pg g − 1 for MBT, 1 pg g − 1 for DBT and 0.4 pg g − 1 for TBT. Linear response range was from 0.02–1260 ng g − 1 for MBT, 0.07–1568 ng g − 1 for DBT and 0.04–2146 ng g − 1 for TBT and RSD < 15% was also obtained. The method was efficiently applied to a real sample sediment from Sado River estuary in Portugal, revealing the existence of BTs pollution, as the TBT level of 189 ± 15 ng g − 1 was much higher than the maximum established as provisional ecotoxicological assessment criteria.

Concentrations of Organotin Compounds in Tissues and Organs of Dugongs from Thai Coastal Waters

Concentrations of butyltin (BT) and phenyltin (PT) compounds were measured in organs and tissues of dugongs (Dugong dugon) from the coastal waters of Thailand. Concentrations of BTs and PTs were in the range of 14-14,468 and <1-30 microg kg(-1)(detection frequency: 79%), respectively. Although concentrations of BTs in dugongs were higher then reported concentrations in cetaceans and pinnipeds, PTs were lower in dugongs. In half of the dugongs in which measurements were made, the concentration of BTs in the liver was the highest among the all the tissues and organs tested. Dibutyltin (DBT) or monobutyltin (MBT) was found to be the dominant compounds among the BTs. The distribution in the body of PTs was not clear because of the lower levels of this compound. TPT was the dominant compound among PTs. The coastal area of Thailand is located off the Gulf of Thailand and the Andaman Sea. Concentrations of organotin (OT) compounds in dugongs collected from the Gulf of Thailand were compared to those from the Andaman Sea. No significant differences in BT or PT concentrations were observed between the two areas (p < 0.05). The concentrations of BTs and PTs in the livers of dugongs were decreased between 1998 and 2002, suggesting a decrease in OT concentrations in the surrounding environment.

Effects of tri butyl tin acetate on dopamine biosynthesis and l-dopa-lnduced cytotoxicity in pc12 cells

The effects of tributyltin acetate (TBTA) on dopamine biosynthesis and L-3,4-dihydroxyphenylalanine (L-DOPA)-induced cytotoxicity in PC12 cells were examined. TBTA at concentrations of 0.1-0.2 microM inhibited dopamine biosynthesis by reducing tyrosine hydroxylase (TH) activity and TH gene expression in PC12 cells. TBTA at 0.1-0.4 microM also reduced L-DOPA (20-50 microM)-induced increases in dopamine content for 24 h in PC12 cells. TBTA at concentrations up to 0.3 microM did not affect cell viability. However, TBTA at concentrations higher than 0.4 microM caused apoptotic cytotoxicity. Exposure of PC12 cells to non-cytotoxic (0.1 and 0.2 microM) or cytotoxic (0.4 microM) concentrations of TBTA with L-DOPA (20, 50 and 100 microM) significantly increased the cell loss and the percentage of apoptotic cells after 24 or 48 h compared with TBTA or L-DOPA alone. These data suggest that TBTA inhibits dopamine biosynthesis and enhances L-DOPA-induced cytotoxicity in PC12 cells.

Selective polymerization of propylene oxide by a tin phosphate coordination polymer

AbstractOligomeric and polymeric polyether polyols, especially poly(propylene oxide), are used for the production of detergents, nonionic surfactants, washing agents, and cleaners, but they are predominantly used in polyurethane production processes. Tin phosphate coordination polymers show good activity in the selective polymerization of epoxides. The catalyst can be easily synthesized by the condensation of tributyl phosphate and butyl tin trichloride. Investigations of this achiral organotin phosphate condensate in the stereoregular polymerization of propylene oxide, including the properties controlling the molecular weight of the resulting poly(propylene oxide) and structural and mechanistic studies, are presented. Additionally, the polymerization of propylene oxide occurs with high activity, no allyl end groups, just a small number of irregularities, and a high percentage of isotacticity (88%) in the polymer. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3032–3041, 2007

The stability of butyltin compounds in a dredged heavily-contaminated sediment

A treatment process for marine sediment heavily contaminated with tributyltin (TBT) was designed that included dehydrating, sunlight drying and dumping processes. The time course in butyltin (BTs) compounds, TBT, dibutyltin (DBT) and monobutyltin concentrations were investigated in the sediment treated under various conditions (light (UV, sunlight and light exclusion), moisture (air-drying and water saturation) and wetting and drying cycles). Significant changes in all the BT compound concentrations with time were not found regardless of the sediment conditions for light and moisture. The results indicated the high stabilities of TBT and DBT in the sediments versus light and moisture condition changes, probably taking place in the treatment process. It is also estimated that the BTs in the sediment are resistant to photo-degradation and biochemical degradation and their half lives are relatively long. In contrast, the decreases in the TBT and DBT were observed during the wetting and drying cycle treatment for the water saturated sediment both during exposure to sunlight and under a dark condition. This result suggested the hypothesis that the TBT degradation could be accelerated by the high microbial activity induced by the moisture changing treatments.

Butyltin in ballast water of merchant ships

The time series of analyzed values indicated that concentration of butyltin (BT) compounds in ballast water varied widely depending on the tanks, depths, and dates of sampling, ranging 4–93 ng l −1 during 7-day voyage. Variations in concentrations of BT in the two ballast tanks corresponded well with the level of BT contamination in different pumping sites of ballast waters. Concentrations of BT species detected in ballast water were rather consistent with those found in port waters and sediment of Taiwan and Japan. This study suggested that the problems concerning BT contamination were neither static nor localized.