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 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.     

Concentration of butyltin species in sediments associated with shipyard activity

Tributyltin (TBT) and dibutyltin (DBT) were analyzed in sediment samples collected from intertidal locations in Portland and Boothbay Harbor, Maine (USA) in 1990 and 1992. Surface sediment TBT concentrations ranged from 24 to 12 400 ng gm(-1) (dry wt basis). Sediments with the highest TBT concentrations were associated with shipyard hull washing/refinishing activities. Analysis of different layers in core samples found that butyltin concentrations decreased with depth at the Boothbay site and remained relatively constant with depth at the Portland site. Elutriate analysis showed that soluble TBT was released from a heavily contaminated sediment. The resulting TBT seawater concentration 1400 ng liter(-1) was < 0.03% of reported seawater solubilities of TBT and was only 0.14% of the total TBT in the sediment sample. This suggests that the TBT in the sediments analyzed is in a bound matrix form, such as paint particles, that releases the biocide slowly. The results indicate that there is a potential for future release of TBT from the resuspension of fine sediments at certain locations in Maine.     

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

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

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.     

Nickel partitioning in formulated and natural freshwater sediments

A natural, field-collected sediment high in organic carbon (OC) and low in acid-volatile sulfide (AVS) was used to evaluate nickel (Ni) complexation to organic matter (OM) over a range of pH under anoxic conditions. It was found that OM strongly influenced Ni partitioning and that Ni complexation to OM was significantly influenced by pH, with complexation increasing with increasing pH (from pH 6 to 8). Using an equilibrium partitioning approach incorporating both [SEM(Ni)]-[AVS] and OC content, lethal and non-lethal toxicity test endpoints were calculated (predicted) and compared to observed toxicity test results using the amphipod, Hyalella azteca, exposed to four Ni-spiked natural sediments varying in OC and AVS content. Generally, lethal and non-lethal toxicity test endpoints were reasonably predictable in low AVS sediments. Due to the apparent lack of equilibrium between dissolved pore-water Ni and the pure Ni sulfide (likely the result of additional dissolved metal binding ligands), and the possible competition of liberated Fe2+ with Ni2+ for binding sites on organic matter, toxicity predictions (based on sediment OC and AVS content) overestimated the combined protective effects of AVS and OC in the sediments containing mid to high (27.87-44.05 micromol/g d.w.) AVS concentrations. Overall, it was found that equilibrium partitioning-based sediment quality guidelines can be improved through the incorporation of nickel complexation to sedimentary OM (in addition to AVS), although further research is required to fully describe nickel-OM interaction.     

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

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

Seasonal variation in the composition and concentration of butyltin compounds in marine fish of Taiwan

For the first time, strong evidence is presented to demonstrate that the accumulations of butyltin compounds (BTs) exhibit seasonal variations with respect to their compositions and concentrations in marine fishes. Measurements were made on the benthic ponyfish Leiogenathus splendens and lizardfish Trachinocephalus myops inhabiting the west coast of Taiwan. In the whole body samples of the ponyfish, BT concentrations ranged from 236 to 2501 ng/g wet wt, with those in winter considerably higher than in the other seasons (p < 0.05 ). In a similar vein, proportions of mono- (MBT), di- (DBT) and tributyltin (TBT) differed significantly (p < 0.001) depending upon the season, with TBT (75 and 50%) dominant in winter and spring and DBT (37 and 57%) and MBT (42 and 24%) dominant in summer and autumn, respectively. In the lizardfish, the concentrations of BTs were one to two orders of magnitude higher in the liver than in the muscle, i.e. 3058-11,473 vs. 36-159 ng/g wet wt, respectively. Concentrations of MBT, DBT and TBT in the muscle ranged, respectively, from 5 to 14, 8 to 35 and 23 to 110 ng/g wet wt, with the major compound being TBT (57-69%) in all seasons. However, in the liver, DBT concentrations, ranging from 992 to 7797 ng/g wet wt, differed seasonally with a descending order of autumn>summer>spring (p < 0.05). Meanwhile, TBT (41%) was predominant in spring, whereas DBT (50 and 68%) was most heavily concentrated in summer and autumn (p < 0.001). Seasonally mediated physiological changes, such as dilution due to growth and metabolic compensation, may play important roles in forming different BT accumulation patterns among seasons and organisms.     

Long-term copper partitioning of metal-spiked sediments used in outdoor mesocosms

Understanding the effects of sediment contaminants is pivotal to reducing their impact in aquatic environments. Outdoor mesocosms enable us to decipher the effects of these contaminants in environmentally realistic scenarios, providing a valuable link between laboratory and field experiments. However, because of their scale, mesocosm experiments are often complex to set up and manage. The creation of environmentally realistic conditions, particularly when using artificially contaminated sediment, is one issue. Here, we describe changes in geochemistry over 1.5 years of a sediment spiked with four different concentrations of copper, within a large freshwater mesocosm facility. The spiking procedure included proportional amendments with garden lime to counteract the decreases in pH caused by the copper additions. The majority of copper within the spiked mesocosm sediments partitioned to the particulate phase with low microgram per liter concentrations measured in the pore waters and overlying waters. The minimum partition coefficient following equilibration between pore waters and sediments was 1.5?×?10⁴ L/kg, which is well within the range observed for field-contaminated sediments (1?×?10⁴ to 1?×?10⁶ L/kg). Recommendations are made for the in situ spiking of sediments with metals in large outdoor mesocosms. These include selecting an appropriate sediment type, adjusting the pH, allowing sufficient equilibration time, and regular mixing and monitoring of metal partitioning throughout the experimental period.     

Trace metals in sediments of two estuarine lagoons from Puerto Rico

Concentrations of As, Cd, Cu, Fe, Hg, Pb and Zn were evaluated in surface sediments of two estuaries from Puerto Rico, known as San José Lagoon (SJL) and Joyuda Lagoon. Significantly higher concentrations in microg/g dw of Cd (1.8 vs. 0.1), Cu (105 vs. 22), Hg (1.9 vs. 0.17), Pb (219 vs. 8), and Zn (531 vs. 52) were found in sediment samples from SJL when compared to Joyuda Lagoon. Average concentrations of Hg, Pb, and Zn in some sediment samples from SJL were above the effect range median (ERM) that predict toxic effects to aquatic organisms. Enrichments factors using Fe as a normalizer, and correlation matrices showed that metal pollution in SJL was the product of anthropogenic sources, while the metal content in Joyuda Lagoon was of natural origins. Sediment metal concentrations found in SJL were comparable to aquatic systems classified as contaminated from other regions of the world.     

Global pollution monitoring of butyltin compounds using skipjack tuna as a bioindicator

Butyltin compounds (BTs) including mono- (MBT), di- (DBT), tri-butyltin (TBT) and total tin (sigmaSn), were determined in the liver of skipjack tuna (Katsuwonus pelamis) collected from Asian offshore waters (off-Japan, the Japan Sea, off-Taiwan, the East China Sea, the South China Sea, off-Philippines, off-Indonesia, the Bay of Bengal), off-Seychelles, off-Brazil and open seas (the North Pacific). BTs were detected in all the skipjack tuna collected, suggesting widespread contamination of BTs even in offshore waters and open seas on a global scale. Considering specific accumulation, Sex-, body length- differences and migration of skipjack tuna did not seem to affect BT concentrations, indicating rapid reflection of the pollution levels in seawater where and when they were collected. Skipjack tuna is a suitable bioindicator for monitoring the global distribution of BTs in offshore waters and open seas. High concentrations of BTs were observed in skipjack tuna from offshore waters around Japan, a highly developed and industrialized region (up to 400 ng/g wet weight). Moreover skipjack tuna collected from offshore waters around Asian developing countries also revealed the levels comparable to those in Japan (up to 270 ng/g wet weight) which may be due to the recent improvement in economic status in Asian developing countries. High percentages (almost 90%) of BTs in total tin (sigmaSn: sum of inorganic tin+organic tin) were found in the liver of skipjack tuna from offshore waters around Asian developing countries. This finding suggests that the anthropogenic BTs represent the major source of Sn accumulation in skipjack tuna from these regions.     

Speciation of heavy metals in estuarine sediments in the northeast of Brazil

An analytical procedure involving a three-step sequential extraction was used to determine the chemical association of heavy metals (Zn, Cr, Mn and Fe) with the major phases (exchangable, reducible and oxidizable) in samples from a fishpond of estuarine sediments. The pond is located in the Capibaribe River estuary, within the boundaries of the city of Recife, in the State of Pernambuco in the northeast of Brazil. The total metal content was determined as well. All metals were extracted from the residual fraction at a percentage greater than 50%.     

Butyltins in estuarine sediments two years after tributyltin use was restricted

The highly toxic compound tributyltin (TBT) is the active agent in many effective antifouling paints. In 1988 the U.S. regulated its use in such paints. Sediments taken from four sites in Boston Harbor, MA., USA in the summer of 1990 were assayed for organotins. There was significantly less TBT at all sites in 1990 than there was in 1988. Dibutyltin (DBT) and monobutyltin (MBT), were also detected, confirming that TBT degradation occurs in the estuary. It is suggested that the decreases are due to biological and/or chemical mechanisms rather than to photochemical reactions or transport away from the sites on resuspended particulate matter.     

Phthalate ester speciation in estuarine water, suspended particulates and sediments

Following earlier work (Al-Omran & Preston, 1987) in which phthalate ester speciation was examined in laboratory studies, the present paper describes the results of an attempt to validate the results by field measurements in the River Mersey Estuary, Liverpool, UK. Samples of water, suspended solids and sediments were analysed for their phthalate ester content. Solid samples were also analysed for their carbon, organic carbon and lipid content. A comparison of the field and laboratory results confirms the association between diethylhexyl phthalate and small particles and shows that other phthalates tend to be associated with relatively coarse, lipid-rich particles. Partition coefficients between dissolved phthalate esters and suspended particles are calculated and compared with other laboratory studies.     

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.     

Polychlorinated organic compounds in Yangtse River sediments

Polychlorinated organic compounds (PCOCs) were analyzed in Yangtse River sediments. The results show that the concentrations of PCOCs in Yangtse River sediments followed the order of DDTs > HCB > HCHs > PCBs. High PCOCs concentrations were detected in sediments from station Y02a and Y02b, which are located in the main input of the Yangtse River (Nanjing section). Results also show that the PCOCs values were highly correlated with organic carbon content and heavy metal contamination.     

Nitromusk compounds in San Francisco Bay sediments

Synthetic nitromusk fragrances are used in a wide variety of consumer products and can enter aquatic environments through wastewater effluent. Although nitromusks are known to be hydrophobic, little attention has been paid to their behavior in sediments. A sediment extraction method using sonication was developed and used to analyze samples from San Francisco Bay. Both musk xylene (MX) and musk ketone (MK) were found at low levels, with mean concentrations of 0.034 and 0.038ngg(-1), respectively. The highest concentrations were found in the southernmost region of the Bay. Samples were also analyzed from a nearby tidal channel fed by a wastewater treatment plant outfall. At this location both musk xylene and musk ketone were found at higher concentrations of 0.13-0.24ngg(-1) MX and 1.08-2.74ngg(-1) MK. A metabolite of musk xylene was also found at levels up to 4.08ngg(-1), suggesting that these metabolites may play an important role in the fate of nitromusk compounds. Concentrations of all three compounds were highest at the earliest of four sampling dates, and a geographic survey of sediments along the tidal channel showed that concentrations decreased rapidly with distance from the outfall and were close to background before the channel reached the Bay.     

Occurrence of butyltin compounds in the waters of selected lakes, rivers and coastal environments from China

The presence of butyltin compounds was investigated for the first time in selected lakes, rivers and coastal environments of China. Aqueous samples were pretreated by the technique of headspace solid phase micro-extraction after hydride generation with sodium tetrahydroborate (NaBH4). Quantitative measurement of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) concentrations were accomplished by capillary gas chromatography with flame photometric detector using quartz surface-induced luminescence. Experimental data demonstrated the widespread occurrence of butyltin compounds in the Chinese aquatic environment. In some locations, the concentrations of TBT were higher than the acute and chronic toxicity threshold of sensitive fresh water or marine organisms. Although DBT and MBT (which mainly come from the degradation of TBT), are less toxic, their occurrence can still affect the ecosystem over a long time frame.     

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.     

Metal contamination and solid phase partitioning of metals in urban roadside sediments

This study was undertaken to assess the anthropogenic impact on metal concentrations of urban roadside sediments (N = 633) in Seoul city, Korea and to estimate the potential mobility of selected metals (Zn, Cu, Pb, Cr, Ni, and Cd) using sequential extraction. Comparison of metal concentrations in roadside sediments with mean background values in sediments collected from first- or second-order streams in Korea shows that Zn, Cu and Pb are most affected by anthropogenic inputs. The 206Pb/207Pb ratios of roadside sediments (range = 1.1419-1.1681; mean 1.1576 +/- 0.0068) suggest that Pb is mainly derived from industrial sources rather than from leaded gasoline. A five-step sequential extraction of roadside sediments showed that Zn, Cd and to a lesser degree Ni occur predominantly in the carbonate bound fraction, while Pb is highest in the reducible fraction, Cu in the organic fraction, and Cr in the residual fraction. It was found that the concentrations in the readily available exchangeable fraction were generally low for most metals examined, except for Ni whose exchangeable fraction was appreciable (average 15.2%). Considering the proportion of metals bound to the exchangeable and carbonate fractions, the comparative mobility of metals probably decreases in the order of Zn > Ni > Cd > Pb > Cu > Cr. As potential changes of redox state and pH may remobilize the metals bound to carbonates, reducible, and/or organic matter, and may release and flush them through drain networks into streams, careful monitoring of environmental conditions appears to be very important. With respect to ecotoxicity, it is apparent the Zn and Cu pollution is of particular concern in Seoul city.