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.     

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.     

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.     

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.     

Horizontal distribution of butyltins in surface sediments from an enclosed bay system, Korea

Tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) compounds were quantitatively determined from surface sediment samples (total 59 stations) covering a whole basin where harbors, shipyards, and aquaculture farms were located. Butyltin compounds were detected from all the stations covering 640 km(2) of an enclosed bay system. TBT concentrations ranged from 4 to 382 ng/g as tin on a dry weight basis, and total butyltin concentrations, from 27 to 1763 ng/g. Horizontal distribution of TBT concentration showed apparent negative gradients from harbors and shipyards, indicating that its contamination was closely related to boating and dry-docking activities. However, TBT concentrations were decreased steeply from source areas. Elevated DBT and MBT levels in creeks imply the possible input of DBT from industrial wastewater. Total butyltin concentrations in sediments are significantly correlated with particulate organic carbon concentration for the subset of stations that are distant from source areas.     

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.     

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.     

Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) distributions in the Bay of Marmara sea: Izmit Bay

In 1999, the concentrations of 16 polycyclic aromatic hydrocarbons (PAHs), the total PAH and polychlorinated biphenyls (PCBs) were measured in sea water, sediment and mussels collected along the coast of Izmit Bay, the most important bay of the Marmara Sea. The total-PAH concentrations, measured by Spectrofluorometry were in the range of 1.16-13.68 microg/l in sea water, in the range of 30.0 1670.0 microg/g dry weight in sediments and in the range from 5.67 to 14.81 microg/g wet weight in edible part of mussel. HPLC revealed Phenanthrene (three rings), chrysene (four rings) and benz[a]antracene (five rings) to be the dominant PAHs in sea water, while 16 different PAHs compounds were observed and measured in mussel samples. The most pollution occured at Dogu Kanali and Dil Deresi where were the main rivers containing wastes fall into the the Izmit Bay. Although the maximum mono-ortho PCB concentrations in sea water were measured in the Dil Deresi River (26.33 ng/l) and the Solventa? (22.19 ng/l) stations, maximum PCB concentrations in mussels were measured in the SEKA (28.11 microg/kg) and the Dil Deresi River (25.68 microg/kg). The dominant congeners of PCBs were from tetra to hexachlorobiphenyls. The toxicity equivalent values were very low in sea water and mussels.     

Distribution of butyltin and derivatives in oyster shells and trapped sediments of two estuaries in Cantabria (Northern Spain)

Distribution of butyltin compounds (BTs) and derivatives (monobutyltin, MBT; dibutyltin, DBT and tributyltin, TBT) was analysed in Crassostrea gigas oyster shells and the sediments trapped in the shell chambers, from two different estuaries in Cantabria (Northern Spain), with very different environmental conditions, where previous data have not been reported. Inorganic tin analysis in oyster shells was performed in order to study the degradation of BTs. Shell thickening and losses in biological growth are related with the presence of TBT, and were determined using three morphological indexes. Total BTs concentrations, expressed as Sn, ranged from 18.0 ng g(-1) to 176.7 ng g(-1) in sediments, and from 2.4 ng g(-1) to 11.1 ng g(-1) in oyster shells. Total inorganic tin concentrations ranged from 1775.0 ng g(-1) to 4781.3 ng g(-1) in oyster shells. The amount of BTs in oyster shells has been associated with the concentrations in the sediments trapped in the shell chambers. Partition coefficients between oyster sediments and oyster shells show the affinity of BTs by the sediments and the higher inorganic tin in oyster shells does not seem to be related to the BTs pollution.     

Butyltin residues in blue mussels (Mytilus edulis) and arkshells (Scapharca broughtonii) collected from Korean coastal waters

Butyltin compounds (BTs) including tributyltin (TBT) and its degradation products, di- (DBT) and mono-butyltin (MBT), were determined in bivalves such as blue mussels (Mytilus edulis) and arkshells (Scapharca broughtonii) collected from Korean coastal waters. BTs were detected in all the blue mussels and arkshells analyzed. The concentrations of total butyltin (sigmaBTs: MBT + DBT + TBT) in blue mussels and arkshells ranged from 49 to 2500 ng/g and 29 to 87 ng/g wet weight, respectively. Higher concentrations of BTs were found in blue mussels collected from Okpo and Kohyonsong Bays and Jangsengpo Harbor where large shipyards and harbors are located with dry-dock facilities. This suggested that maritime activities nearby the harbors play a major role as the source of BTs. Concentrations of TBT in mussels collected from Korea were one of the highest values reported, suggesting ongoing TBT contamination in Korea. Among BTs, TBT was the predominant compound both in blue mussels and arkshells collected from almost all the sampling locations, indicating the fresh input of TBT in Korean coastal waters. Smaller mussels tended to accumulate BTs at higher concentrations than larger ones, which may be due to higher filtration rate of small mussels and/or contact with surface microlayer in intertidal zones.     

Organotin contamination in the Atlantic Ocean off the Iberian Peninsula in relation to shipping

Imposex in female snails, a bioindicator of TBT contamination, and the presence of organotins in snails' tissue and sediments were studied at nine sites off the western Iberian Peninsula. The study was part of a European project (acronym HIC-TBT) co-financed by the EU-LIFE programme, intending to investigate and communicate the impact of organotins from ships in marine ecosystems. Snails and sediments were sampled during two cruises in May/June 1999 and in January 2000 in areas of high, intermediate and low-shipping density. Imposex was found in female snails from several sampling sites, some of which had an imposex incidence of 100%. Differences in sensitivity were found between species; hence comparison of imposex levels between locations where different species were collected was not straightforward. Total organotin concentrations in sediments (sum of butyl and phenyltin compounds) ranged from 21 to 185 ng Sn g(-1) with higher values for most sites sampled in the vicinity of shipping lanes. Organotin concentration in snails' tissue ranged from <5 to 196 ng Sn g(-1), which are similar to those found in snails from other offshore areas contaminated by TBT. Overall, these results give further support to the recent ban on the use of organotin based antifouling paints to all ship size.     

Organo-tins in sediments and mussels from the Sado estuarine system (Portugal)

Analyses of methyl- and butyl-tin levels in freshwater, estuarine and marine sediments from the Sado estuarine system, and in mussels (Mytilus galloprovincialis) from its adjacent coast, have been performed in order to detect the contaminated areas. The main inputs of tributyl-tin (TBT), along with degradation products di- and monobutyl-tin (DBT and MBT), were detected in the estuarine zone, due to high discharge from shipyards located in this area. These levels are sometimes very high, ranging from 235 to 12,200 ng g(-1) total butyl-tins in sediments. Such inputs lead to higher bioconcentration values in mussels in the estuarine zone, as well as in a harbour located along the adjacent coast. The bioconcentration of organo-tins in mussel tissues could be enhanced in estuarine turbid waters, due to an ingestion of butyl-tins adsorbed onto fine particles, in comparison with non-turbid coastal waters. Debutylation processes occur in both sediments and mussel tissues; in organisms, these processes may lead to the formation of inorganic tin, which may be methylated differently according to the period of the year.     

Distribution patterns of nitrobenzenes and polychlorinated biphenyls in water, suspended particulate matter and sediment from mid- and down-stream of the Yellow River (China)

Samples of water, suspended particulate matter (SPM) and sediment were collected from mid- and down-stream of the Yellow River. The distribution and concentration of 10 nitroaromatic compounds and polychlorinated biphenyls (PCBs) were extensively studied. The total concentration of 10 nitrobenzenes (SigmaNBs) varied from 0.269 to 9.052 microg l(-1) in water, from 2.916 to 164.4 microg kg(-1) dry weight in SPM, and from 0.954 to 14.72 microg kg(-1) dry weight in sediment. PCBs associated with the sediments, measured as the summed responses of Aroclor 1242, 1248, 1254, 1260 (in comparison to those of a standard 1:1:1:1 mixture), were found to be in the range of non-detectable to 5.98 microg kg(-1). In the samples collected, various PCB congeners showed similar distribution characteristics with congeners containing 3-5 chlorine atoms accounting for more than 96.4% of total PCB. In most of the samples, PCB concentrations occurred in the order: TetraCB > TriCB > PentaCB. Levels of SigmaNBs in the Yellow River were relatively low in comparison with values reported from other river and marine systems, and PCB levels were comparatively low. Relative to the PCBs, SigmaNBs showed significantly more difference among the various stations, presumably due to the influence of different pollution sources. No obvious correlation was observed between the pollutant concentrations and either the TOC or the grain size of the sediments.     

The long-term environmental behaviour of strontium and barium released from former mine workings in the granites of the Sunart region of Scotland, UK

The concentrations of strontium and barium have been measured in water, sediment and the shells of mussels (Mytilus edulis) from a river system in the Sunart region of Scotland, UK. The aim was to establish the fate and mobility of these elements, which are slowly being released from old mine workings on the Strontian granites. Enhanced strontium (1500-2000 microg l(-1) and 250-290 microg l(-1)) and barium concentrations (316 microg l(-1) and 83 microg l(-1)) were found in the waters originating from the two mine drains studied. Both element were also found at significant levels in the river sediments taken from the vicinity of each drainage site (Sr: 225 microg g(-1) and 120-125 microg g(-1); Ba: 1380 microg g(-1) and 126-170 microg g(-1)). The data suggests that the sediments are acting as a reservoir for these group II cations from where they become distributed throughout the river system. Strontium is found to be incorporated into the shells (3.16-3.46 microg g(-1)) and pearls (3.57 microg g(-1)) of the blue mussel, located at the estuarine margin some 10 km downstream, at values close to the maximum expected (3.3% by weight of the calcium content). The study presents a view of the fate of barium and strontium in a river system over a prolonged period of time. As such it provides valuable information for studies that seek to model the impact of the accidental release of barium and strontium (including the important radionuclide 90Sr) into the environment.     

Pilot survey of a broad range of priority pollutants in sediment and fish from the Ebro river basin (NE Spain)

Priority organic pollutants were investigated in sediments and fish collected along the Ebro river basin (NE Spain) to evaluate their occurrence, transport and bioavailability. Sediments were collected in 18 sites and two species of fish were captured in nine sites according to the availability in each area. The sampling sites covered industrial, urban and agricultural areas. Four methods were used to detect 20 organochlorine compounds (OCs), 8 polycyclic aromatic hydrocarbons, 3 organotin compounds, 2 alkylphenols and 40 polybrominated diphenyl ethers (PBDEs) from purified extracts. The contamination pattern was site specific and no downstream increase in concentration of pollutants was observed but rather a generalized low level diffuse pollution. Target compounds were detected in sediments at 0.01 to 2331 microg/kg dry weight, and only OCs and PBDEs were accumulated in benthopelagic fish. Toxicological assessment was performed according to predicted environmental levels and revealed sites where adverse effects could occur.     

Assessment of organotin pollution along the Polish coast (Baltic Sea) by using mussels and fish as sentinel organisms

Levels of tributyltin (TBT) and its degradation products, mono- (MBT) and dibutyltin (DBT), as well as triphenyltin (TPT), were monitored in 10 stations along the Polish coast (Baltic Sea). Mussel-Mytilus edulis-and fish-Platichthys flesus-were used as sentinel organisms. The bioaccumulation patterns of butyltin and phenyltin compounds varied substantially. Butyltins were detected in mussel tissue from all the sampled stations. Among them, organisms from the Gulf of Gdansk showed the highest residues (68 ng/g w.w. as Sn) in conjunction with elevated TBT/DBT ratios, which suggest recent inputs of TBT in the area. Additionally, flatfish were sampled in the Gulf of Gdansk, and different tissues (liver, digestive tube and gills) were analyzed separately. TPT, although undetected in mussels, was always present in fish. The highest organotin concentration was observed in the liver (369 ng/g w.w. as Sn) of fish caught near Gdansk port. Relatively high concentrations were observed in digestive tube, which points out the ingestion of organotin contaminated food as an important uptake route of those compounds in P. flesus.     

Concentrations of organotin compounds in sediment and clams collected from coastal areas in Vietnam

Levels of butyltin (BT) and phenyltin (PT) compounds were determined in sediments and clam Meretrix spp. collected from north and central coastal areas in Vietnam. Concentrations of TBT in sediments ranged from 0.89 to 34 ng g(-1) dry wt and those in clams ranged from 1.4 to 56 ng g(-1) wet wt. The levels of TBT in sediments and clams from Vietnam were within limits reported from other countries. Further, the TBT level in clams was lower than the tolerable average residue level (TARL) estimated based on tolerable daily intake (TDI). Trace amounts of PTs were also found in both sediment and clam samples. In sediments from north and central Vietnam, the concentrations of TBT were highest in the order of Hue (28 ng g(-1) dry wt), Cua Luc (15 ng g(-1) dry wt), Sam Son (6.3 ng g(-1) dry wt), and Tra Co (5.5 ng g(-1) dry wt). Among the clams from north and central Vietnam, the levels of TBT in clams from Cua Luc were dramatically high at 47 ng g(-1) wet wt. TBT formed the principal butyltin species in sediment at all sites studied. The ratios of TBT in sediment were higher among BT compounds at all study sites. Of total BTs, TBT was the dominant species in clams from almost all sites studied. In spatial distribution, TPT showed a pattern similar to TBT, suggesting the use of TPT as an antifouling paint. The partition coefficient between sediment and calms was calculated. The partition coefficients of TBT and TPT were 2.01 (0.56-5.5) and 9.23 (3.1-20), respectively. These results show that sediment-bound TBT is a source of contamination to clams in addition to dissolved TBT.     

Pesticide levels in surface waters in an agricultural-forestry basin in Southern Chile

Residues of five pesticides in surface water were surveyed during 2001 and 2003 in the Traiguen river basin in Southern Chile. Simazine, hexazinone, 2,4-D, picloram herbicides and carbendazim fungicide were selected through a pesticide risk classification index. Six sampling stations along the river were set up based on agricultural and forestry land use. The water sampling was carried out before and after the pesticide application periods and in correspondence to some rain events. Pesticides were analyzed by HPLC with DAD detection in a multiresidue analysis. During 2001, in the first sampling campaign (March), the highest concentrations of pesticides were 3.0 microg l(-1) for simazine and hexazinone and 1.8 microg l(-1) for carbendazim. In the second sampling (September), the highest concentration were 9.7 microg l(-1) for 2,4-D, 0.3 microg l(-1) for picloram and 0.4 microg l(-1) for carbendazim. In the last sampling period (December), samples indicated contamination with carbendazim fungicide at levels of up to 1.2 microg l(-1). In sampling carried out on May 2003, no pesticides were detected. In October 2003, the highest concentrations of pesticides were 4.5 microg l(-1) for carbendazim and 2.9 microg l(-1) for 2,4-D. Data are discussed in function of land use and application periods of the products, showing a clear seasonal pattern pollution in the Traiguen river. Risk assessment for these pesticides was calculated by using a risk quotient (RQ = PNEC/PEC). For picloram the calculated RQ < was 0, which indicates that no adverse effects may occur due to the exposure to this herbicide in the Traiguen river basin. For 2,4-D, simazine, hexazinone, carbendazim RQ > 1, meaning that adverse effects could occur and it is necessary to reduce pesticide exposure in surface waters. It is recommended to continue with a pesticide monitoring program and the implementation of ecotoxicological testing with local and standardized species in order to consider the probability of effects occurrence, with less uncertainty. Thus, it will be more feasible to make some recommendations to regulatory agencies regarding the pesticide use.     

Organotin compounds and polychlorinated biphenyls of livers in squid collected from coastal waters and open oceans

The current status of global marine pollution by TBT (tributyltin), TPT (triphenyltin) and polychlorinated biphenyls (PCBs) was examined by determining their concentrations in squid livers. TBT and TPT concentrations in squid livers were higher in coastal waters than in open oceans. The highest values of TBT and TPT of 279 and 519 ng g(-1), respectively, were detected off Japan. TBT concentrations were higher in the northern hemisphere than those of the southern hemisphere organisms. TPT was not detected in squid livers collected in the southern hemisphere. The variation in TBT and TPT concentrations between the northern and the southern hemisphere was greater than those recognized for PCBs distribution in the world oceans. This global distribution pattern of TBT, TPT and PCB seemed to reflect their usage (amount, period and manner of utilization). Approximate TBT concentrations in seawater estimated from bioaccumulation factor in the squid liver were 0.1-5.8 ng litre(-1) in waters around Japan, tr-0.8 ng litre(-1) in oceanic waters in the northern hemisphere, and tr-0.4 ng litre(-1) in the southern hemisphere oceans.     

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.