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Determination of triorganotin species in water samples by liquid chromatography-electrospray-mass spectrometry.

Liquid chromatography coupled to electrospray-mass spectrometry (LC-ES-MS) with positive ion detection was evaluated for the determination of tributyltin and triphenyltin in water samples using tripropyltin as internal standard. The separation was performed in the isocratic mode on a silica-based C18 column with a mobile phase containing 0.02% trifluoroacetic acid in acetonitrile-water (50:50, v/v). The optimum LC-ES-MS conditions were established and quantification was performed on the basis of the [M]+ ions. Limits of detection for standard solutions were 100 and 200 pg Sn injected for triphenyltin and tributyltin, respectively, and good reproducibility was observed. Solid-phase extraction was carried out on C18 cartridges to preconcentrate the analytes from natural water samples, with recoveries ranging from 80 to 110%. Limits of detection for SPE-LC-ES-MS were in the range of low ng l(-1), which demonstrates the suitability of the method for environmental samples.

Chromatography, Liquid↗

Rapid determination of butyltin species in water samples by multicapillary gas chromatography with atomic emission detection following headspace solid-phase microextraction.

A procedure for the rapid determination of mono-, di- and tributyltin in water samples is described. The analytes are simultaneously ethylated and concentrated on a solid-phase microextraction fibre placed in the headspace over the sample for 2 min. The ethylated species are then separated and selectively quantified in only 90 s using a multicapillary gas chromatography column combined with atomic emission detection. The influence of blank signals and sampling conditions on the sensitivity of the method is described. Detection limits of 1-5 ng/l and relative standard deviations of 6-10% at concentrations of 20 ng/l were obtained.

Chromatography, Gas↗

Occurrence and effects of organotins on adult common whelk (Buccinum undatum) (Mollusca, Gastropoda) in harbours and in a simulated dredging situation.

Transplanted common whelk (Buccinum undatum) (Mollusca, Gastropoda) accumulated fairly high levels of organotins (tributyltin (TBT) and triphenyltin (TPT)) during exposure in three harbours with different TBT contamination. This did not though lead to an increase in imposex frequency in the adult females studied. Simulating harbour dredging in an experiment using suspended sediment from one of the harbours only resulted in a low concentration of TBT in the tissues of the common whelk and subsequently no changes in the occurrence and degree of imposex. The common whelk seemed to receive the main part of TBT from the water column and the limited bioaccumulation in the experiment indicates that desorption of TBT from the suspended sediment was slow. After TBT has been totally banned, dredging of contaminated sediments will cause increased exposure of the biota to TBT. Due to slow desorption the increase may however, be slight and temporary to pelagic and epibenthic species unless the settled particles are resuspended.

Animals↗

Contamination of the coastal waters of Bermuda by organotins and the triazine herbicide Irgarol 1051.

A study of the distribution of the 'booster' biocide 2-methylthio-4-tert-butylamino-6-cyclopropyl amino-s-triazine (Irgarol 1051) was carried out in the coastal waters of Bermuda. Irgarol 1051 concentrations (as determined by GC/MS) up to 590 ng l-1 have been measured within Hamilton Harbour. The data presented herein unequivocally demonstrate contamination of the coastal system of Bermuda by Irgarol 1051. Concurrently, TBT concentrations were measured and results indicate that levels are falling through legislated changes in antifouling treatments, from 220 ng l-1 in 1990 to < 20 ng l-1 (as Sn) by 1995, in the open water area of Hamilton Harbour. Concentrations of TBT immediately offshore from a boatyard were found to be > 600 ng l-1 (Sn), indicating continuing release due to painting operations and sediments in the area.

Bermuda↗

Assessment of organotin contamination in marine sediments and biota from the Gulf and adjacent region.

Butyltin species were measured in sediments from coastal locations in the Gulf and Gulf of Oman. Both butyltin and phenyltin species were measured in biota samples from four countries in this region. With tributyltin (TBT) concentrations up to 60 ngSng(-1), some sediments could be classified as contaminated (i.e. TBT>1.3 ngSng(-1)), namely Dukhan (Qatar), the BAPCO industrial complex and Askar (Bahrain), and Hilf and the Raysut Port Area (Oman). Higher concentrations of total butyltins were found in oysters relative to fish, but ranging from 6.5 to 488 ngSng(-1) dry weight they are nonetheless relatively low. Diphenyltin and triphenyltin were found in some fish and bivalves from the Gulf, but not in biota from the Gulf of Oman. The environmental levels of organotin species are comparatively low by global standards and pose no immediate public health problems.

Animals↗

Effects of butyltins on human 5alpha-reductase type 1 and type 2 activity.

Butyltins are widely used biocides and accumulate in the food chain. Tributyltin is an imposex-inducing endocrine disrupter in animals. Imposex is characterized by the development of additional male sex organs on females. In a previous study, we identified tributyltin as an inhibitor of human cytochrom P450 aromatase activity. The present work focuses on the impact of butyltins on human androgen metabolism. Activation of androgens is mediated by two human 5alpha-reductase isoenzymes. 5alpha-Reductase type 1 was completely inhibited by tributyltin chloride (IC50=19.9 microM) and dibutyltin dichloride (IC50=32.9 microM), whereas 5alpha-reductase type 2 was only inhibited by tributyltin chloride (IC50=10.8 microM). Both isoenzymes were not affected by tetrabutyltin or monobutyltin indicating that at least two butyl groups bound to the positively charged Sn are required for the interaction of butyltins with the enzymes. Tributyltin inhibited 5alpha-reductase type 1 competitively whereas an irreversible inhibition was evident for the type 2 isoenzyme. In contrast to the distinct effects on 5alpha-reductases, reductive brain 17beta-hydroxysteroid dehydrogenase activity was not inhibited by any butyltin. Insufficient activation of androgens is responsible for developmental disorders of the male reproductive system such as hypospadias. At pharmacologic levels butyltins might contribute to the onset of developmental disorders of the male reproductive system. At present, however, it is unknown whether these levels are reached after acute or chronic exposure to butyltins.

3-Oxo-5-alpha-Steroid 4-Dehydrogenase↗

Occurrence of butyltin residues in sediment and mussel tissues from the lower-most Tennessee River and Kentucky Lake, U.S.A.

Surface sediments and mussel samples were collected at six selected locations in the lower-most Tennessee River and Kentucky Lake, U.S.A. and analyzed for butyltin (BT) derivatives. In sediments, total BT concentrations ranged from 6.8 to 356 ng g-1 dry wt. A wide range of concentrations in sediments suggested the presence of localized area of contamination. In mussel tissues, total BT concentrations varied between 26-107 ng g-1 dry wt. BT levels were comparable to the levels reported in mussels from some coastal sites as well as a few freshwater ecosystems. Leaching of tributyltin-containing anti-fouling paints in the ocean-going ships is a source of tributyltin, and discharge of municipal sewage and industrial waste waters in to this watershed may account for the presence of the monobutyltin and dibutyltin derivatives detected in the samples. To our knowledge, this is the first report on the butyltin concentrations in sediment and mussel tissues from the lower-most Tennessee River and Kentucky Lake.

Animals↗

Butyltins in shellfish, finfish, water and sediment from the Coos Bay estuary (Oregon, USA).

Butyltin was measured in tissue, water and sediment samples collected throughout Coos Bay estuary between 1986 and 1997. Butyltin-induced shell deformation in commercial oysters prompted this assessment. Butyltins are released from tributyltin oxide (TBTO)-containing boat paint. Clams from three sites contained tributyltin (TBT) levels ranging from 168 to 457 microg/kg in 1992-1994. Consequently, Oregon Health Division (OHD) issued a shellfish consumption advisory in 1995; it was rescinded in 1997 after US Environmental Protection Agency (EPA) revised the TBTO oral reference dose (RfD). The revised RfD changed the tissue screening level from 112 to 1120 microg TBT/kg. Fifty percent of sediment samples collected during 1991-1997 and analyzed for total butyltins (TotBT) exceeded the Puget Sound Dredge Disposal Analysis Screening Level (PSDDA SL) of 73 microg TBT/kg dw. TotBT at three shipyards selected for site assessment by EPA ranged from 24 to 68,613 microg/kg dw. Sediment and tissue butyltins have been decreasing in all but one area of the estuary.

Animals↗

A review of organotin regulatory strategies, pending actions, related costs and benefits.

Achieving consensus on equitable and effective national and global regulation(s) for the use of organotins as biocides in antifouling boat bottom paints has proven to be very complex and difficult for a variety of reasons as discussed in this paper. There appears to be broad agreement among stakeholders about the effectiveness of tributyltin (TBT) in antifouling paints. A draft Assembly Resolution prepared by the Marine Environmental Protection Committee (MEPC) of the International Maritime Organization (IMO) to propose a global ban on the use of organotins in antifouling paints was approved by the IMO at its 21st regular session (November 1999). In approving the Resolution, the Assembly agreed that a legally binding instrument (global convention--an international treaty) be developed by the Marine Environmental Protection Committee that should ensure by 1 January 2003, a ban on the application of tributyltin (TBT)-based antifouling paints; and 1 January 2008 as the last date for having TBT-based antifouling paint on a vessel. The Assembly also agreed that a diplomatic conference be held in 2001 to consider adoption of the international legal instrument. Monitoring, policing, enforcement, fines and record-keeping are yet to be defined. In addition, the MEPC has also proposed that IMO promotes the use of environmentally-safe anti-fouling technologies to replace TBT. Existing national regulations in the US and Europe have: (1) restricted the use of TBT in antifouling boat bottom paints by vessel size (less than 25 m in length), thus eliminating TBT from the smaller and recreational vessels that exist in shallow coastal waters where the impacted oysters species grow; (2) restricted the release rates of TBT from co-polymer paints; and (3) eliminated the use of free TBT in paints. The present movement toward a global ban suggests that the above regulatory approach has not been sufficient in some countries. Advocates of the ban cite international findings of: (1) higher levels of TBT in surface waters of ports and open waters; (2) imposex still occurring and affecting a larger number of snail species; (3) TBT bioaccumulation in selected fisheries; and (4) the availability of 'comparable' alternatives (to TBT) with less environmental impact. The global ban has been absent of a policy debate on the: (1) lack of 'acceptable and approved' alternatives in many nations; (2) appreciation of market forces in nations without TBT regulations; (3) full consideration of the economic benefits from the use of TBT; (4) 'acceptance' of environmental impacts in marinas, ports and harbors; and (5) realization of the 'real' time period required by ships for antifoulant protection (is 5-7 years necessary or desirable?). Estimates of fuel savings range from $500 million to one billion. In assessing the environmental impact from TBT, there are two sources: the shipyard painting vessels and the painted vessel itself. Today vessels can be painted with regulated or banned antifouling materials by boatyards in a country that does not have TBT regulations and subsequently travel in international and regulated national waters and thus bringing the impact back to the country which was trying to prevent it. Worse, local and national regulations for TBT have proven to be the antithesis of the popular environmental cliché--'Think Globally and Act Locally.' Legislative policies enacted by 'regulated' countries to regulate the use of TBT to protect (their) local marine resources have subsequently had far reaching environmental and economic impacts which have in essence transferred TBT contamination to those countries least able to deal with it. Market forces are selective for cheap labor and cheap environments. 'Unregulated' countries have unknowingly accepted the environmental and human health risks to gain the economic benefits from painting TBT on ships. (ABSTRACT TRUNCATED)

Cost-Benefit Analysis↗

Caprella watch: a new approach for monitoring butyltin residues in the ocean.

A comparative study on the butyltin levels in various organisms showed that marked bioaccumulation occurs in certain lower trophic levels; i.e. from seawater to phytoplankton and into caprellid amphipods, Caprella spp. Caprella spp., which inhabit algal communities and aquaculture beds in the subtidal zone, are small crustaceans with reduced movement and a life-span of less than 3 months. These characteristics indicate that Caprella spp. may be well-suited for monitoring butyltin residue changes over small spatial and temporal scales. Two groups of organisms, mussels and neogastropods, have been mainly used for monitoring butyltin in shallow water ecosystems. These invertebrates mainly inhabit the intertidal zone where the butyltin levels vary widely depending on the immersion period and exposure to the sea surface microlayer. Monitoring using neogastropods may also over estimate exposures after restrictions on tributyltin, since neogastropods show an irreversible response to residue changes owing to their long life-spans. Thus, we propose usage of Caprella spp. to monitor temporal and spatial changes in baseline concentrations of butyltins.

Animals↗

Increasing imposex in populations of Bolinus brandaris (Gastropoda: Muricidae) in the northwestern Mediterranean.

The muricid gastropod Bolinus brandaris exhibited imposex, a phenomenon linked to the use of organotin biocides. Several stages of imposex development (1-5) could be distinguished and were documented with SEM-photographs for the first time in this species. Additional alterations of the genital tract in females (blocked vulva preventing copulation and deposition of egg capsules) and males (excrecences on the penis and vas deferens) were shown. Imposex intensity on the Catalan coast was very high. The frequency of imposex off Barcelona and Vilanova i la Geltrú was 100%, with all females showing stage 4. Imposex frequency off Sant Carles de la Ràpita was 99.7% and the VDS index scored 3.9. Despite regulations of TBT-containing antifouling paints in Spain since 1990, the present study revealed that frequency and intensity of imposex have increased on the Catalan coast, at least since 1997. However, at present, imposex does not apparently affect the population dynamics of B. brandaris in the studied area, since no serious consequences on female reproduction (only one case of female sterilization) were detected. Gonadal activity and oogenesis were not suppressed or supplanted by spermatogenesis. Sex ratios were not male-biased. Possible sources of organotin biocides are examined.

Animals↗

Cytochrome P450 differences in normal and imposex-affected female whelk Buccinum undatum from the open North Sea.

Normal and imposex-affected female Buccinum undatum were sampled from the open North Sea at three locations, one with low, and two with high shipping densities. Cytochrome P450 components and P450 aromatase activity were determined in the microsomal fractions isolated from pooled digestive gland/gonads. Cytochrome P450 aromatase activity was significantly higher (P < 0.05) in normal females collected in the low shipping density area (1,325 +/- 295 fmol/h/mg protein) than levels from imposex animals from a high shipping density area (620 +/- 287 fmol/h/mg protein). A negative correlation was found between aromatase activity and organotin body burden (r = -0.99). Levels of CYP450, cytochrome b5 and NADPH cytochrome c reductase activity did not show differences among groups. This is the first field evidence of depressed aromatase activity in imposex affected females, although additional research under laboratory controlled conditions is required to fully understand the mechanisms underlying the development of imposex in this species.

Animals↗

Tributyltin and triphenyltin induce spermatogenesis in ovary of female abalone, Haliotis gigantea.

Two-month flow-through exposure experiments of tributyltin (TBT) and triphenyltin (TPhT) were conducted with abalone, Haliotis gigantea. Nominal concentrations of 100 ng TBT/l and 100 ng TPhT/l caused significant spermatogenesis in ovaries of exposed females. There were also significantly more contracted primary oocytes observed in females exposed to either TBT or TPhT than controls. The incidence of two types of unknown cells was also significant in females exposed to TPhT. No significant histological changes were observed in testis of exposed males. This ovarian spermatogenesis caused by TBT and/or TPhT resembles gastropod imposex. Remarkably high concentrations of TBT and TPhT were observed in the head (including central nervous system ganglia), compared to muscles concentrations. Accumulation of TBT and TPhT in the head may disturb reproductive hormonal regulators through neuropeptides released from ganglia. This, as well as possible aromatase inhibition, may be one of the inducers for spermatogenesis in the abalone ovaries.

Animals↗

Imposex in the rock shell, Thais clavigera, as evidence of organotin contamination in the marine environment of Korea.

Imposex was measured in the rock shell, Thais clavigera, from the coast of the Korean peninsula. Frequency of imposex was 0% at two reference sites, but at 47 out of 61 sites, frequency of imposex was recorded as 100%. The degree of imposex was relatively high at the sites near a harbor and a shipyard. Tributyltin (TBT) and triphenyltin (TPT) concentrations in T. clavigera ranged from 5 to 508 ng/g and from 3 to 2460 ng/g, respectively. A significant positive relationship was found between degree of imposex and organotin concentration, whereas a significant negative relationship was obtained between female-to-male sex ratio and the degree of imposex. During a field transplantation of T. clavigera from a pristine area to a port, TBT and TPT were accumulated in T. clavigera, and imposex was induced. T. clavigera shows considerable potential as a bioindicator species of the adverse effects of TBT and TPT contamination.

Animals↗

Cellular and molecular effects of trimethyltin and triethyltin: relevance to organotin neurotoxicity.

Many of the neurotoxic aspects of organotin exposure have been described. Organotin exposure culminates in its accumulation in the CNS and PNS. The clinical picture is dominated by neurological disturbances; yet, the primary basis for their neurotoxicity is unknown. Trimethyltin (TMT) is primarily a CNS neurotoxin affecting neurons within the hippocampal pyramidal band and the fascia dentata. Triethyltin (TET) is a neurotoxin that produces a pathological picture dominated by brain and spinal cord edema. The first part of this review summarizes the current understanding of the interaction of TMT and TET with biologically active sites in the induction of neurotoxicity. In the second part, several hypotheses for the differential neurotoxic effects of these organotins and their shortcomings are discussed.

Animals↗