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.     

Occurrence of organotin compounds in water and sediment in Canada

Water and sediment samples from 265 locations across Canada were analyzed for butyltin and methyltin species, and inorganic tin. In 10% of the water samples the highly toxic tributyltin species was found at concentrations which could cause growth retardation upon chronic exposure to a sensitive organism, rainbow trout yolk sac fry. High concentrations of tributyltin were found in some sediments (up to 10 mg Sn/kg dry weight), but the biological availability of sediment-associated tributyltin is unknown. Tributyltin was mainly found in areas of heavy boating and shipping traffic, which is consistent with its use as an antifouling agent in some paints for boats, ships and docks. The methyltin species were found much less frequently in water and sediment than tributyltin and its degradation products.     

Butyltin concentrations in oysters from the Gulf of Mexico from 1989 to 1991

Oyster samples from 53 Gulf of Mexico coastal sites were collected and analyzed for butyltins during 1989, 1990, and 1991. The geometric-mean tributylin concentrations were 85, 30, and 43 ng Sn/g for 1989, 1990, and 1991, respectively. The tributyltin concentrations are best represented by a log-normal distribution. A decline in the butyltin concentrations at sites with relatively low butyltin concentrations for 1989 compared with 1990 and 1991 was observed, and, at relatively high butyltin concentrations (> 400 ng Sn/g), there was hardly any difference between 1989 and 1991, but lower concentrations were present in 1990. Continued monitoring is needed in order to determine if butyltin contamination of the coastal marine environment is decreasing in response to use limitations.     

Impact of industrial and mine drainage wastes on the heavy metal distribution in the drainage basin and estuary of the Sado River (Portugal)

This paper presents results from a survey of the heavy metal distribution in sediments in the drainage basin and estuary of the Sado River (Portugal). In the drainage basin, heavy metals originate mostly from pyrite outcrop erosion and mining activities (Cd, Zn, Cu and locally Hg, Pg), and also from crust erosion (Sn, Ni, Ti, Zr). These sources are not correlated with the particulate organic carbon (POC) and so the metals are thought to be in inorganic forms in this area. Anthropogenic heavy metal sources (urban and industrial) are found in the lower estuary (Sn, Cd, Hg, Zn, Pb and Cu) along with high POC concentrations. In this zone, these metals are thought to be strongly adsorbed onto organic particles. Furthermore, organo-metallic species are likely to be present, as demonstrated in the case of Sn, since methyl- and butyl-tin species were detected in sediments from this area. This suggests the need for the detection of organo-metallic species to understand the heavy metal geochemical cycles. No long-term changes in metal concentrations are found in sediment cores, except in the middle estuary (Zn, Cu) due to the development of mining activities on an industrial scale in the 1860s.     

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.     

Contamination of butyltin compounds in Malaysian marine environments

Concentration of butyltin compounds (BTs), including tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) and total tin (SigmaSn) were determined in green mussel (Perna viridis), 10 species of muscle fish and sediment from coastal waters of Malaysia. BTs were detected in all these samples ranging from 3.6 to 900 ng/g wet wt., 3.6 to 210 ng/g wet wt., and 18 to 1400 ng/g dry wt. for mussels, fish and sediments, respectively. The concentrations of BTs in several locations of this study were comparable with the reported values from some developed countries and highest among Asian developing nations. Considerable concentration of BTs in several locations might have ecotoxicological consequences and may cause concern to human health. The parent compound TBT was found to be highest than those of its degradation compounds, DBT and MBT, suggesting recent input of TBT to the Malaysian marine environment. Significant positive correlation (Spearman rank correlation: r2=0.82, P<0.0001) was found between BTs and SigmaSn, implying considerable anthropogenic input of butyltin compounds to total tin contamination levels. Enormous boating activities may be a major source of BTs in this country, although aquaculture activities may not be ignored.     

Organotin compounds in precipitation, fog and soils of a forested ecosystem in Germany

Organotin compounds (OTC) are highly toxic pollutants and have been mostly investigated so far in aquatic systems and sediments. The concentrations and fluxes of different organotin compounds, including methyl-, butyl-, and octyltin species in precipitation and fog were investigated in a forested catchment in NE Bavaria, Germany. Contents, along with the vertical distribution and storages in two upland and two wetland soils were determined. During the 1-year monitoring, the OTC concentrations in bulk deposition, throughfall and fog ranged from 1 ng Sn l(-1) to several ten ng Sn l(-1), but never over 200 ng Sn l(-1). The OTC concentrations in fog were generally higher than in throughfall and bulk deposition. Mono-substituted species were the dominant Sn species in precipitation (up to 190 ng Sn l(-1)) equaling a flux of up to 70 mg Sn ha(-1) a(-1). In upland soils, OTC contents peaked in the forest floor (up to 30 ng Sn g(-1)) and decreased sharply with the depth. In wetland soils, OTC had slightly higher contents in the upper horizons. The dominance of mono-substituted species in precipitation is well reflected in the contents and storages of OTC in both upland and wetland soils. The ratios of OTC soil storages to the annual throughfall flux ranged from 20 to 600 years. These high ratios are probably due to high stability and low mobility of OTC in soils. No evidence was found for methylation of tin in the wetland soils. In comparison with sediments, concentrations and contents of organotin in forest soils are considerably lower, and the dominant species are less toxic. It is concluded that forested soils may act as sinks for OTC deposited from the atmosphere.     

Effects of experimental acidification on mobilisation of metals from sediments of limed and non-limed lakes

In order to study the influence of pH on the mobilisation of metals from lake sediments, intact sediment cores with overlying water were sampled from one lime treated lake and one acidified lake. The overlying water of two cores from each lake was successively acidified to pH 4.2 over a period of 3 months. In the acid treated samples from the limed lake, the initial concentrations of Al, Cd, Mn, Pb and Zn in the overlying water were generally lower and the final concentrations were higher than in the acid treated samples from the acidified lake. The labile inorganic fraction of Al (Al(i)) was increasingly dominating as pH decreased. Redox potential and pH in the sediment indicated that the upper two centimetres were involved in the exchange reactions. The experiment showed that mobilisation of metals from sediments can occur and the results indicated that mobilisation could contribute to increased concentrations of metals in lake water during reacidification of formerly lime treated lakes.     

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.     

Variations of alkaline phosphatase activity and P fractions in sediments of a shallow Chinese eutrophic lake (Lake Taihu)

The distribution of alkaline phosphatase activity (APA) and P fractions in sediment cores and the relationship between them were studied in a shallow Chinese freshwater lake (Lake Taihu). Sediment cores were collected from four sites, characterized by different degrees of eutrophication in June 2004. Sediment P was fractionated into Fe/Al-P, Ca-P, organic P (OP), inorganic P (IP) and total P (TP). The former two species made the largest contribution to the sediment P pool. Results show that trophic status and hydrological conditions have great impact on the APA of the sediments. The order of the APA in sediments was conjectured to be: macrophyte dominated lake>transitional lake>algal dominated lake. APA profiles follow a similar downcore decreasing trend. There was a positive relationship between the APA and the TP, IP. The multiple linear regression equation of the APA and P fractions is: APA=-97+0.768TP-0.985Fe/Al-P.     

GC determination of butyltins in natural waters by flame photometric detection of hexyl derivatives with mass spectrometric confirmation

Butyltin compounds in the 1–100 ng Sn/Liter range are solvent extracted from estuarine waters and derivatized with n-hexyl magnesium bromide. This forms tetraalkyltins that are quantified by gas chromatography with flame photometric detection and confirmed by gas chromatography mass spectrometry. The n-hexyl derivatives of methyltin and butyltin species are easily separated, and quantified relative to an internal standard, tripentyltin chloride.     

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.     

Accumulation of butyl- and phenyltin compounds in starfish and bivalves from the coastal environment of Korea

Triphenyltin (TPT) and tributyltin (TBT) concentrations were determined in two starfish species (Asteria pectinifera and Asterias amurensis), bivalves (Crassostrea gigas or Mytilus edulis), and seawater samples from sites around the coasts of Korea. Both TPT and TBT concentrations in starfish ranged from 8 to 1560 ng/g and from <2 to 797 ng/g as Sn on a dry weight basis, respectively. TPT concentration accounted for 75.4% and 86.4% of total phenyltin concentration in A. pectinifera and A. amurensis, respectively, while monobutyltin, a degradation product of TBT, accounted for 86.3% and 57.2% of total butyltin, respectively. Triphenyltin concentrations in A. pectinifera were significantly correlated to water and bivalve TPT concentrations, which implies that dietary uptake of TPT from contaminated prey as well as direct uptake from surrounding water contribute to TPT body residues in the starfish. Starfish could be target organisms for monitoring TPT compound in the marine environment, due to their high accumulation and low degradation capacity towards TPT.     

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.     

Butyltin compounds in sediment and fish from the Polish Coast of the Baltic Sea

Concentrations of mono- (MBT), di- (DBT), and tri-(TBT) butyltin compounds were measured in eggs, liver, and muscle of nine species of fish from four regions of the Baltic Sea - the Firth of Vistula, the Gulf of Gdańsk, Puck Bay, and the mouth of the Vistula River. The overall concentration ranges among all the fish sampled from the four sites were: < 7 to 79 ng/g for MBT, 6 to 1100 ng/g for DBT, 7 to 3600 ng/g for TBT, and 16 to 4800 ng/g for total BTs, on a wet wt basis. The highest concentration of total BTs was found in herring liver from the Firth of Vistula (4800 ng/g, wet wt) and in roach muscle from Puck Bay (3300 ng/g, wet wt), while the least concentration was found in burbot eggs and liver from the Vistula River (39 and 32 ng/g, wet wt, respectively). TBT was the major form of BTs present in most samples analyzed. Sediment samples collected from shipyards in the Gulf of Gdańsk contained butyltin concentrations ranging from 1.2 to 46 μg/g (dry wt) for MBT, 2.0 to 42 μg/g for DBT, and 2.6 to 40 μg/g for TBT. As with the fish, the majority of the BTs in sediment were present as TBT, which suggested recent exposure of the aquatic environment of the region to TBT.     

In situ experiments for element species-specific environmental reactivity of tin and mercury compounds using isotopic tracers and multiple linear regression

The fate of mercury (Hg) and tin (Sn) compounds in ecosystems is strongly determined by their alkylation/dealkylation pathways. However, the experimental determination of those transformations is still not straightforward and methodologies need to be refined. The purpose of this work is the development of a comprehensive and adaptable tool for an accurate experimental assessment of specific formation/degradation yields and half-lives of elemental species in different aquatic environments. The methodology combines field incubations of coastal waters and surface sediments with the addition of species-specific isotopically enriched tracers and a mathematical approach based on the deconvolution of isotopic patterns. The method has been applied to the study of the environmental reactivity of Hg and Sn compounds in coastal water and surface sediment samples collected in two different coastal ecosystems of the South French Atlantic Coast (Arcachon Bay and Adour Estuary). Both the level of isotopically enriched species and the spiking solution composition were found to alter dibutyltin and monomethylmercury degradation yields, while no significant changes were measurable for tributyltin and Hg(II). For butyltin species, the presence of light was found to be the main source of degradation and removal of these contaminants from surface coastal environments. In contrast, photomediated processes do not significantly influence either the methylation of mercury or the demethylation of methylmercury. The proposed method constitutes an advancement from the previous element-specific isotopic tracers’ approaches, which allows for instance to discriminate the extent of net and oxidative Hg demethylation and to identify which debutylation step is controlling the environmental persistence of butyltin compounds.     

The tail feathers of osprey nestlings (Pandion haliaetus L.) as indicators of change in mercury load in the environment of southern Sweden (1969-1998): a case study with a note on the simultaneous intake of selenium

The tail feathers of 104 osprey nestlings (Pandion haliaetus) from Lake Asnen, southern Sweden, were analyzed for total mercury and selenium content. Concentrations of mercury in feathers from the western part of the lake fell during the period 1969-1998, when pollution from industrial mercury had decreased and a paper mill upstream of the lake was closed down in 1979. Nestlings from the eastern part of the lake had initially lower levels of mercury, predominantly from atmospheric fallout. The levels did not decrease during the period. The reason for the differences seems to be the limited water flow between the western and the eastern part of the lake. The selenium concentrations were constant over time and approximately the same in both parts of the lake. The total-Hg/Se ratio in the western part of the lake was 2.94, which is somewhat higher than the 1:1 molar ratio constant (2.54). This indicates that the bioaccumulated quantity of selenium which is thought to be protective for the organisms against the toxic effects of mercury, is somewhat insufficient to bind all body mercury.     

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.     

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: Zió?kowskiego, Siarkowe, Wi?lane, Weglowe, Chemików and Paliw P?ynnych Quays. The cores of 25cm 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 <0.063mm. The dominant fraction in whole sediment, i.e. fraction grain diameter <2.00mm, was sand (grain diameter 2.00-0.063mm). 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 <2.00mm fraction were 2144.9, 434.7 and 148.1ngSng(-1)d.w., respectively, while the corresponding mean values in the <0.063mm fraction were 6556.4, 1593.7 and 450.0ngSng(-1)d.w. The mean concentrations of monophenyltin (MPhT) have been estimated at 29.0 and 49.9ngSng(-1)d.w. for the <2.00 and <0.063mm 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 (Wi?lane, Weglowe Quays) contained the highest concentrations of BT and PT.     

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.