Butyltins in water, biofilm, animals and sediments of the west coast of India

Biofilm, fish, oyster, mussel, clam, surface seawater, suspended particulate matter (SPM), and sediment samples were collected from marine and/or estuarine waters of the west coast of India. These samples were analysed for butyltin derivatives such as dibutyltin (DBT) and tributyltin (TBT). The concentrations DBT plus TBT varied between 2.4 and 8.3, 163 and 363 ng/l, 5 and 2853 ng/g dry wt in the SPM, seawater and sediment samples, respectively, of the Marmugao harbour. The values of DBT plus TBT ranged between 0.60 and 29, 123 and 242 ng/l and 1.4 and 65 ng/g dry wt in SPM, water and sediment samples, respectively, collected from the Mandovi estuary. In the Dona Paula Bay the DBT plus TBT varied from 10 to 89 ng/l in surface seawater, and TBT from 10 to 513 ng/g in biofilm samples. For the coastal sediment samples the concentration of DBT plus TBT ranged between 36 and 133 ng/g dry wt of sediment. For the animal samples the DBT plus TBT ranged between 58 and 825 ng/g dry wt of the tissue. Mussel tissues contained the highest amount of DBT plus TBT (825 ng/g dry wt tissue), whereas highest TBT concentration was recorded in the oyster (732 ng/g dry wt). TBT was generally the most abundant butyltin compound in most of the samples suggesting fresh inputs and/or less degradation of TBT. A wide range of the observed butyltin concentrations suggests the presence of localized areas of contamination. Leaching of tributyltin-containing antifouling paints from the ocean going ships, fishing and recreational boats, barges, and the inputs of TBT from the Goa shipyard and dry dock facility situated in the harbour are the probable sources of the DBT and TBT in the samples of the west coast of India. Higher levels of TBT were observed in biofilm relative to that in the surrounding seawater. When fed on TBT contaminated biofilm of the diatom Navicula subinflata, butyltin concentrations in the clam Paphia malabarica increased over the period of feeding suggesting the importance of biofilm in the transfer of butyltins to higher group of organisms.     

Transplacental transfer of butyltins to fetus of Dall's porpoises (Phocoenoides dalli)

Here we provided evidence, for the first time, on the placental transfer of butyltin species in Dall's porpoise (Phocoenoides dalli). The maternal to fetal transfer of butyltins including monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT) was investigated in a mother-fetus pair collected off the Sanriku coast of Japan. The maternal individual was found contaminated as its liver accumulated the highest concentrations of all MBT, DBT and TBT. This study revealed that the transfer rate was about 0.3% for total butyltins to a fetus of about 6 months old. Unlike in the mother, the fetal liver does not appear to be a preferential organ for accumulation of all the butyltins. In a approximately 100 kg-weight mother Dall's porpoise and its fetus of 2.21 kg-weight about 1,269 microg (TBT, 578 microg; DBT, 480 microg; MBT, 211 microg) and 4.2 microg of total butyltins (TBT, 1.1 microg; DBT, 2.1 microg; MBT, 0.96 microg) were found, respectively.     

In-situ partitioning of butyltin compounds in estuarine sediments

The in-situ solid/pore-water partitioning of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) was determined for an estuarine sediment profile collected from a commercial marina. Total butyltin levels exceeded sediment quality guideline values, and were 220-8750 microg/kg for TBT, 150-5450 microg/kg for DBT and 130-4250 microg/kg for MBT. Pore-water butyltin concentrations ranged from 0.05 to 2.35 microg/l for TBT, 0.07-3.25 microg/l for DBT, and 0.05-0.53 microg/l for MBT. The partitioning of butyltin compounds between the sediment solid-phase and pore-water was described by an organic carbon normalised distribution ratio (D(OC)). The observed D(OC) values were similar for TBT, DBT and MBT, and were 10(5)-10(6) l/kg. Values for the Butyltin Degradation Index (BDI) were larger than 1 at depths greater than 10 cm below the sediment/water-column interface. This indicates that substantial TBT degradation has occurred in the sediments, and suggests that natural attenuation may be a viable sediment remediation strategy.     

Butyltin compounds in sediment and molluscs from the shipping strait between Denmark and Sweden

The distribution of tributyltin (TBT) contamination in the subtidal zone of the waters between Denmark and Sweden was investigated in relation to major international shipping lanes. Sediment and different benthic molluscs were sampled in transects along and perpendicularly to the shipping lanes in the Sound (?resund) and the Kattegat/Skagerrak region. The samples were analysed for TBT and its degradation products, dibutyltin (DBT) and monobutyltin (MBT), using GC-PFPD. In sediments, the TBT concentration ranged from <1 to 19 ng g(-1) dry weight (dw) with a strong correlation between the TBT concentration and the organic fraction in sediment (r(2)=0.90) in the samples collected in the Sound, where the highest concentrations were found. This relationship was not observed in the samples from the Kattegat because the TBT concentration in most sediment samples was below the limit of detection. In the molluscs, TBT and its degradation products were detected in all samples from the entire area with concentrations ranging from 8.1 ng g(-1) dw in Buccinum undatum to 1316 ng g(-1) dw in Nuculana pernula. The deposit-feeding bivalve N. pernula was found to have a particularly high accumulation potential for TBT. In addition, a strong correlation between TBT concentrations in sediment and N. pernula was found. Therefore this species seems to be an ideal organism for monitoring sediment contamination. The TBT concentration in N. pernula was found to decrease gradually along the shipping lanes from the Sound, through the Kattegat and into the Skagerrak.     

Bioaccumulation of butyltins in Dreissena polymorpha at a confined placement facility in Buffalo, New York

This study involves a site characterization followed by biomonitoring with the zebra mussel, Dreissena polymorpha, at the Times Beach confined placement facility (CPF), located in Buffalo, NY. The contaminant of interest was tributyltin (TBT) and the degradation products dibutyltin (DBT) and monobutyltin (MBT). At study initiation (Day 0) TBT levels in the baseline mussels were 5.86 +/- 0.43 ng Sn/g, DBT levels were 2.25 +/- 0.37 ng Sn/g. No MBT was detected in the Day 0 baseline samples. Caged reference mussels placed back in the Black Rock Channel Lock and retrieved on Days 19 and 34 had TBT, DBT, and MBT levels which did not differ significantly from the Day 0 baseline levels. Mussels placed at the Times Beach CPF had TBT concentrations that were significantly lower at both Days 19 (3.65 +/- 0.90 ng Sn/g) and 34 (3.50 +/- 1.03 ng Sn/g) than the Day 0 baseline analysis (5.86 +/- 0.43 ng Sn/g). The results of this study indicate that butyltins were detected at the CPF site in the sediment (7.33 +/- 5.70 ng Sn/g) but not the water column (not detected at 0.01 microgram/l). In this study the zebra mussel was able to depurate TBT even in the presence of contaminated sediment. TBT may be bioaccumulated from the sediments. However, the initial levels in the mussels were so high, levels actually dropped as sediment-tissue equilibria levels were reached by the mussels.     

Butyltins in sediments from Boston Harbor, USA

Sediments from 12 sites in Boston Harbor were assayed for butyltins. The highest levels of tributyltin (TBT) were found at sites where commercial or pleasure boats were moored, where ocean going vessels dock, and at a former shipyard. Little or no TBT was detected at sites which do not have a history of significant boating activity. Dibutyltin and monobutyltin were also detected at most sites, indicating that degradation of TBT occurs at these sites.     

Survey of organotin compounds in rivers and coastal environments in Portugal 1999-2000

In the period from April 1999 to May 2000, organotin pollution, namely butyl and phenyltins, was investigated in coastal and continental waters (46 stations), estuarine sediments (15 stations) and mussels (Mytilus galloprovincialis) (13 stations) throughout Portugal. Sampling points were chosen in areas of specific industrial, agricultural and harbor activities. Butyltins (BTs) were the only tin species identified of which tributyltin (TBT) was found in the whole area. Concentrations of TBT in river water ranged from 3 to 30 ng L(-1) (as Sn), marine sediment ranged from 4 to 12 microg kg(-1) (as Sn), whereas concentrations in mussel tissue ranged from 2.5 to 490 microg kg(-1) (as Sn). Given that some water samples appeared to be contaminated by higher monobutyltin (MBT) and dibutyltin (DBT) concentrations, the role of biological degradation and direct inputs from agricultural and industrial applications areas are discussed. The study compares depleted butyltin pollution in sediments and mussels of the Portuguese coastline associated with antifouling paints with previously reported levels. Inputs in river waters are more related to (i) PVC leaching and (ii) industrial sources, in some cases discharged by municipal wastewaters.     

Contamination of butyltin and phenyltin compounds in the marine environment of Otsuchi Bay, Japan

Butyltin (BT) and phenyltin (PT) compounds were measured in seawater, sediment, and biological samples collected from coastal areas of Otsuchi Bay, Japan. Tributyltin (TBT) compounds in seawater, sediment, plankton, mussels, scallops and fish were in the range of 0.008-0.074 microg liter(-1), 0.01-0.64 mg (kg dry wt)(-1), 0.24-9.8 mg (kg dry wt)(-1), 0.04-0.18 mg (kg wet wt)(-1), 0.10-0.13 mg (kg wet wt)(-1) and 0.01-0.02 mg (kg wet wt)(-1), respectively. Trace amount of PTs were found in seawater. The highest concentrations of TBT and triphenyltin (TPT) were found near a shipyard. Triorganotin compounds were more dominant than their metabolites. A positive correlation was observed between the concentrations of TBT and TPT in the mussels. Concentrations of TBT and TPT in mussels were high in the upper intertidal zone, and decreased toward the water.     

Experimental effects of tributyltin (TBT) contaminated sediment on a range of meiobenthic communities

Microcosm experiments have been carried out with whole natural meiobenthic communities to look at the effects of TBT sediment contamination on the community structure of the dominant nematode component of the meiobenthos. TBT has a high affinity for aquatic sediments, yet this is the first study of the effects of this contaminant in sediment on natural benthic communities. Three communities were studied from contrasting locations in south-west England: the intertidal of the Lynher estuary (muddy sediment) and the Exe estuary (sandy sediment) and the subtidal (50m depth) at Rame Head off Plymouth (muddy sand). Fresh sediment with natural meiobenthic communities was incubated for 2 months with TBT-contaminated sediment (three dose levels) in bottles. Nematodes were identified and enumerated and subjected to multivariate data analysis. The sandy Exe estuary fauna was significantly affected by TBT-contaminated sediment at all three doses (0.3, 0.6 and 0.9 microg g(-1) dry wt (as Sn) sediment), whereas the offshore fauna from Rame Head was significantly affected only at the highest dose. The muddy Lynher estuary meiofauna was affected (somewhat peculiarly) at the medium dose level only. Meiobenthic nematodes may not be as sensitive to TBT-contaminated sediment as other infaunal benthos but exhibited responses to levels of contamination still persisting in some UK estuaries and harbours. Comparing the effects of TBT with those of copper and zinc in the same laboratory experiments, our observations suggest that the relative impact of TBT on meiobenthic community structure is not as great as these contaminants in marine sediments. Although there are very few observations of TBT toxicity in sediment, it appears that TBT is toxic at much lower concentrations in seawater (ppb) than it is in sediment (ppm).     

Flame retardants, surfactants and organotins in sediment and mysid shrimp of the Scheldt estuary (The Netherlands)

Sediment and mysids from the Scheldt estuary, one of the largest and most polluted estuaries in Western Europe, were analyzed for a number of contaminants that have been shown to possess endocrine-disrupting activity, i.e. organotins, polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA), nonylphenol ethoxylates (NPE) and transformation products, nonylphenol (NP) and nonylphenol ether carboxylates (NPEC). In addition, in vitro estrogenic and androgenic potencies of water and sediment extracts were determined. Total organotin concentrations ranged from 84 to 348 ng/g dw in sediment and 1110 to 1370 ng/g dw in mysid. Total PBDE (excluding BDE-209) concentrations ranged from 14 to 22 ng/g dw in sediment and from 1765 to 2962 ng/g lipid in mysid. High concentrations of BDE-209 (240-1650 ng/g dw) were detected in sediment and mysid (269-600 ng/g lipid). Total HBCD concentrations in sediment and mysid were 14-71 ng/g dw and 562-727 ng/g lipid, respectively. Total NPE concentrations in sediment were 1422 ng/g dw, 1222 ng/g dw for NP and 80 ng/g dw for NPEC and ranged from 430 to 1119 ng/g dw for total NPE and from 206 to 435 ng/g dw for NP in mysid. Significant estrogenic potency, as analyzed using the yeast estrogen assay, was detected in sediment and water samples from the Scheldt estuary, but no androgenic activity was found. This study is the first to report high levels of endocrine disruptors in estuarine mysids.     

Tributyltin distribution and producing androgenic activity in water,sediment, and fish muscle

This study investigated the concentrations of Tributyltin (TBT) in water, sediment, and fish muscle samples taken from Kaohsiung Harbor and Kaoping River estuary, Taiwan. TBT concentrations in water and sediment samples ranged from less than 18.5 to 34.1 ng Sn L^?1 and from 2.44 to 29.7 ng Sn g^?1 weight per weight (w/w), respectively. Concentrations in the TBT‐contaminated fish muscle samples ranged from 10.8 to 79.6 ng Sn g^?1 w/w. The TBT concentrations in fish muscle were higher than those in water and sediment samples. The fish muscle/water TBT bioconcentration factor (BCF) ranged from 590 to 3363 L kg^?1. Additionally, the water samples were assessed for androgenic activity with an MCF7‐AR1 human breast cancer cell line. The androgenic activity ranged from 0.94 to 3.1 ng‐dihydrotestosterone per litre water (ng‐DHT L^?1). Higher concentrations of TBT in water and sediment samples occurred in the dry season, but the androgenic activity had higher values in the rainy season.     

Contamination by butyltin compounds and organochlorine residues in green mussel (Perna viridis, L.) from Thailand coastal waters

In order to elucidate marine pollution by butyltins and organochlorine residues in coastal waters of Thailand, green mussels (Perna viridis) were collected in 1994 and 1995 and analyzed. Butyltin compounds, such as tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT), were detected in most mussel samples, ranging from 4 to 800 ng g(-1) wet wt (as total). The composition of butyltin derivatives in green mussel was in the order of TBT > DBT > MBT. The results indicated that butyltin contamination was widespread, particularly in high boating areas and in coastal aquaculture facilities. Concentrations of organochlorine residues were much lower than of butyltin compounds. Among organochlorine residues examined, dichlorodiphenyltrichloroethane compounds (DDTs) were found to be the highest, followed by polychlorinated biphenyls (PCBs) > chlordane compounds (CHLs) > hexachlorocyclohexanes (HCHs) > hexachlorobenzene (HCB). To our knowledge, this is a first report on the detection of butyltin residues in Thailand coastal waters.     

Tributyltin partitioning in sediments: effect of aging

The effect of aging on the solid/pore-water partitioning and desorption behaviour of tributyltin (TBT) in sediments was examined. Three sediment samples with contrasting physical and chemical properties were spiked with 10 mg/kg TBT and aged under sterile conditions for periods of time ranging from 1 to 84 days. Aging had a negligible effect on partitioning and desorption behaviour in a sandy sample with very low organic carbon content (0.2% w/w). In contrast, for samples with larger amounts of organic carbon (2.6% and 4.8% w/w), aging caused substantial increases in TBT sorption. For these samples, apparent distribution coefficients (KD,app) obtained from sequential 2 h desorption experiments also exhibited a twofold increase between spiked sediments subjected to aging for 1 day and 84 days. This study demonstrates that aging effects may be an important aspect of TBT fate in contaminated sediments.     

Butyltins in sediments from Santa Monica and San Pedro basins, California

Butyltins have been measured for the first time in sediments from the deeper waters of the Santa Monica and San Pedro (SM/SP) basins of Southern California borderland. Core samples were collected from water depths ranging from 458 m in the shelf to 906 m in the central basin. Surficial and a few subsurface sections from selected cores were analyzed for butyltins. The dominant components are generally dibutyl and monobutyltins (DBT and MBT, respectively). Microbial degradation of Tributyltin (TBT, the most toxic of the butyltin species) to DBT and MBT during the long range transport to deeper basins, as well as a lack of continuing inputs of TBT in the present times could justify the butyltins signatures found in the region. The levels of butyltins are in the lower range (below detection level, <1, to 14 ng of Sn g(-1)) relative to nearshore sediments. However, the results demonstrate that the butyltins are, indeed, found even in the sediments of the central basins of the Southern California borderland suggesting that deeper global oceanic regimes need to be further investigated for these compounds.     

Occurrence of polychlorinated naphthalenes, polychlorinated biphenyls and short-chain chlorinated paraffins in marine sediments from Barcelona (Spain)

Polychlorinated naphthalenes (PCNs), short-chain chlorinated paraffins (SCCPs) and polychlorinated biphenyls (PCBs) were analysed in marine sediment samples collected from the coastal area of Barcelona (Spain) and near of a submarine emissary coming from a waste water treatment plant located at the mouth of the Besòs River (Barcelona). An integrated sample treatment based on Soxhlet extraction followed by a simple clean-up with Florisil and graphitized carbon cartridge was employed. Gas chromatography coupled to ion-trap tandem mass spectrometry (GC-MS/MS) and gas chromatography-mass spectrometry in electron capture negative ionization mode, were used for PCN and SCCP determinations, respectively, while for PCB analysis gas chromatography with electron capture detection (GC-ECD) was used. The method developed provided low limits of detection (0.001-0.003 ng g(-1) dry weight (dw) for PCNs, 1.8 ng g(-1) for SCCPs and 0.006-0.014 ng g(-1)dw for PCBs) and good run-to-run precisions (lower than RSD 8%) for the analysis of sediment samples. Concentration levels ranging from 0.17 to 3.27 ng g(-1)dw for PCNs, between 0.21 and 1.17 microg g(-1)dw for SCCPs, and from 2.33 to 44.00 ng g(-1) (dw) for PCBs, were found in the coastal sediments, while for samples collected near to the submarine emissary higher levels (from 2.02 to 6.56 ng g(-1)dw for PCNs, between 1.25 and 2.09 microg g(-1)dw for SCCPs and from 22.34 to 37.74 ng g(-1)dw for PCBs) were obtained. The results obtained provide new data about the occurrence of PCN and SCCP in the coastal area of Barcelona.     

Three decades of tributyltin in the coastal environment with emphasis on Arcachon Bay, France

This account briefly reviews the fate, bioconcentration and effects of tributyltin (TBT) three decades after its introduction into the coastal environment. Data on TBT-related events that occurred in Arcachon Bay (gastropod imposex, oyster recruitment failure, oyster shell malformations, concentrations in water and sediments) are revised and reinterpreted. Historically, TBT concentrations in the waters of the open bay seldom exceeded 1 ng Sn l(-1) in the 1960s, likely surpassed the range of 100 ng Sn l(-1) from 1977 to 1981 (years when no oyster spat were collected and the local shellfish industry collapsed), and decreased to about 1 ng Sn l(-1) in the late 1980s and early 1990s following legislation in January 1982 banning TBT use. TBT pollution is discussed in relation to the green tides that have developed in Arcachon Bay since 1982.     

Assessment of tin and butyltin species in estuarine superficial sediments from Gipuzkoa,Spain

Ten superficial sediments from river estuaries of Gipuzkoa (North Spain) were collected and analyzed for nine metals (including tin, Sn) and butyltin compounds (monobutyltin, MBT; dibutyltin, DBT; tributyltin, TBT). Total metal concentration in the fine fraction (<63 micrometer) of the sediment was determined in aqua regia--hydrofluoric acid extracts by atomic absorption spectrometry. The butyltin species (BTs) were firstly extracted from the sediments with hydrochloric acid-methanol mixture. After derivatization with sodium tetraethyl borate, the organotin compounds were extracted by solid phase microextraction (SPME) in headspace mode. A fiber coated with 100 micrometer poly(dimethylsiloxane) was used for SPME. The organotin species were analyzed by gas chromatography-flame ionization detection. Analysis of the certified reference sediment (PACS-2) shown the suitability of the procedures for determination of metal contents and DBT-TBT species in contaminated sediments. Factorial analysis was used to examine the main sources of metals. Three factors represented more than 89% of the total variance of the metal system, and the Sn was related with Cu-Zn-Pb suggesting the same pollution source. The BTs concentrations in the area were high (TBT ranged from 0.05 to 5.48 mg Sn kg(-1)). The percentage of total butyltin species ( summation operator BTs) respect to the total Sn amount was higher than 4% in all the sediments, showing in the Bidasoa river estuary a remarkable value higher than 20%. Hence, the studied estuarine sediments reflect a pollution that is related with historical industrial and fishing activities of the area.     

Levels and distributions of polybrominated diphenyl ethers,hexabromocyclododecane, and tetrabromobisphenol A in sediments from Taihu Lake,China

The concentrations and distribution of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), and tetrabromobisphenol A (TBBPA) were investigated in 28 sediment samples collected from Taihu Lake, Eastern China. The results showed that all three classes of compounds were detected in 28 sediment samples but that PBDEs were the main contaminants in the study area. The total PBDE concentrations ranged from 3.77 to 347 ng/g dry weight (dw) with a mean value of 72.8 ng/g dw, whereas the concentrations ranged from 0.168 to 2.66 and from 0.012 to 1.30 ng/g dw for HBCD and TBBPA, respectively. In all of the sediment samples, BDE-209 was the predominant congener, accounting for 95.9 to 98.6 % of the total PBDEs, which indicated that commercial mixtures of deca-BDEs were the main sources of PBDE contamination. Higher concentrations of PBDEs were found in samples collected from Meiliang Bay and Gonghu Bay near the inflow river, which suggested that inflow runoff might play an important role in the PBDE levels in Taihu Lake sediments.     

Tributyltin in environmental samples from the Former Derecktor Shipyard, Coddington Cove, Newport RI

Tributyltin (TBT) was detected in all 24 surface sediment (top 2 cm) samples collected from Coddington Cove, Newport, RI. TBT surface sediment concentrations ranged from 32 to 372 ng Sn/g with a mean concentration of 146 ng Sn/g. Analyses of selected core sections detected TBT in at least the top 18 cm at all 7 stations where cores were collected. No consistent TBT concentration trends with depth for these cores suggest mixing is an important process in the sediment column. In one core (station 28), TBT was found in the 76-86 cm section at a concentration of 141 ng Sn/g; thus sediments are a significant sink for TBT. However, sediment mixing processes can enhance releases of bioavailable TBT. Mussels, clams and fish from Coddington Cove contain TBT at concentrations ranging from 9.2 to 977 ng Sn/g. TBT concentrations in lobsters were below the detection limit (<6 ng Sn/g). Based on available screening criteria, TBT concentrations in Coddington Cove sediment is likely to be having an adverse effect on the biota at some locations.     

Butyltins in muscle and liver of fish collected from certain Asian and Oceanian countries

Concentrations of butyltin residues were determined in muscle tissue of fish collected from local markets and sea food shops in India, Bangladesh, Thailand, Indonesia, Vietnam, Taiwan, Australia, Papua New Guinea and the Solomon Islands. Contamination levels were determined in the Asia-Pacific region and human exposure was estimated. Similarly, corresponding liver samples of fish muscle collected in Australia, Papua New Guinea and the Solomon Islands were analyzed to obtain information on partitioning of butyltin compounds between muscle and liver tissues. Butyltin compounds were detected in most of the samples which suggested widespread contamination in Asia and Oceania. The concentrations of butyltin compounds were, on average, an order of magnitude higher in liver than in muscle. Residue concentration of Sigmabutyltin in liver was found to be correlated significantly (p < 0.02) with those in muscle. Intensive ship-scrapping activities, sewage disposal and antifouling paints are considered the major sources of butyltins in this region. Increased proportions of MBT over DBT and TBT in samples from most locations indicated degradation of TBT to MBT in fish tissues during storage at 4 degrees C in the dark over 1-2 years. The possibility that fish have been subject to increased exposure to MBT and that TBT degrades to MBT quite rapidly in tropical environments are also considered. Butyltin concentrations in fish from Asia and Oceania were lower than those reported for Japan, Canada and the USA. Although the number of samples analyzed from each country was small, it is tentatively suggested that intake of butyltins by humans via consumption of fish in these countries was < 25% of the tolerable daily intake of 250 ng kg bw(-1) day(-1). To our knowledge, this is the first study reporting on butyltin pollution in developing Asian countries.