Emission to air of volatile organotins from tributyltin‐contaminated harbour sediments

An analytical method for determining the presence in air of volatile forms (e.g. chlorides) of tributyltin (TBT) and that of methylbutyltins Me _nBu_(4?n)Sn (n = 1–3) was developed and used to establish whether dredged harbour sediments contaminated with TBT served as sources of air pollution with respect to organotin compounds. The method was based on active sampling of the air being analysed and sorption of analytes onto Poropak‐N. Sorbed methylbutyltins were extracted with dichloromethane and analysed by gas chromatography using flame photometric detection. Other butyltins were converted into butyltin hydrides prior to analysis by gas chromatography. It was shown that TBT‐contaminated sediments from Marsamxett Harbour, Malta, placed in 0.5 l chambers through which air was displaced by continuous pumping for 11 days released mainly methylbutyltins, with concentrations (as tin) reaching maximum 48 h mean values of 8.7 (Me₃BuSn), 22.1 (Me₂Bu₂Sn) and 93.0 ng m^?3(MeBu₃Sn) being measured. Other volatile forms of TBT, dibutyltin and monobutyltin were detected in the headspace air, but very infrequently and at much lower tin concentrations (<2 ng m^?3). It was also shown that methylbutyltins dissolved in sea‐water ([Sn] = 0.2 to 400 ng l^?1) were very difficult to exsolve from this medium, even on prolonged evaporation of the solutions using mechanical agitation and active ventilation. The results suggest that emission of methylbutyltins from contaminated sediments probably occurs only from the surface of the material. The environmental implications of these findings in the management of TBT‐polluted harbour sediments are discussed. Copyright © 2002 John Wiley & Sons, Ltd.     

Toxicity of butyltin,phenyltin and inorganic tin compounds to sulfate‐reducing bacteria isolated from anoxic marine sediments

The toxicity of butyltin, phenyltin and inorganic tin compounds to three pure strains of sulfate‐reducing bacteria (SRB), isolated from a tributyltin (TBT)‐polluted sediment, was determined. The isolated strains were identified as belonging to the genus Desulfovibrio. A new toxicological index (GR₂₅) was developed to assay the toxicity of organotin compounds. Deleterious effects on suspended anaerobic cell cultures were observed for concentrations ranging between 500 and 600 µM for tin tetrachloride, 55 and 260 µM for triorganotins, 30 and 90 µM for diorganotins, and 1 and 6 µM for mono‐organotins. Whereas the number of substituents influenced the toxicity of organotins, the type of substituent (butyl or phenyl) proved to have little or no impact. Trisubstituted compounds (tributyl‐ and triphenyl‐tin) were less toxic to these strains of SRB than the monosubstituted forms (monobutyl‐ and monophenyl‐tin). This is the opposite trend to that currently reported for aerobic organisms. Under the given anoxic conditions, the toxicity of organotin compounds obtained yielded a significant negative correlation with the total surface area (TSA) of the tested molecules. Comparison of the TBT toxicity data observed for different microbial groups suggests that the tolerance of bacteria to organotin compounds might be related to organotin–cell wall interactions as well as to aerobic or anaerobic metabolise pathways. Copyright © 2000 John Wiley & Sons, Ltd.     

Imposex in Sea Snails,Caused by Organotin (Tributyltin and Triphenyltin) Pollution in Japan: a Survey

A country-wide survey and laboratory experiments on imposex (a superimposition of male sex organs on female sea snails) in Japanese sea snails were carried out: 38 species were observed to be affected by imposex. For the rock shell, Thais clavigera , the percentage occurrence of imposex was 100% at almost all sites surveyed. The degree of imposex seemed to be positively correlated with the concentrations of tributyltin (TBT) and triphenyltin (TPT) in the species. The results of laboratory experiments showed that imposex in T. clavigera was initiated and promoted by both TBT and TPT. Many oviduct-blocked individuals, which were thought to be sterile, were observed in T. clavigera at sites near marinas and harbours. The effects of organotin pollution on the population of T. clavigera were observed at the sites near marinas. From the results of the additional country-wide survey on imposex in T. clavigera during 1993–1995, serious organotin pollution and imposex symptoms in the species are still continuing in Japan. © 1997 by John Wiley & Sons, Ltd.     

Interdisciplinary study for the evaluation of biochemical alterations on mussel <Emphasis Type="Italic">Mytilus galloprovincialis</Emphasis> exposed to a tributyltin-polluted area

An interdisciplinary approach was employed to monitor the concentration and the effects of butyltin compounds in mussels (Mytilus galloprovincialis). Tissues from animals exposed to a marine area (Vado Ligure harbour) with a high concentration of tributyltin (TBT) were analysed and compared with control samples. TBT concentrations were measured by gas chromatography–mass spectrometry and the protein pattern in gill tissues was studied by proteomic analysis. Several proteomic signatures associated with contaminant exposure were observed; spots that were significantly increased in all contaminated samples were identified by mass spectrometry as fragments of β-tubulin. The degradation of β-tubulin was then confirmed by western blot analysis with specific anti-β-tubulin antibody. The effects observed on mussel gills after exposure in the TBT-polluted area are discussed.     

Determination of organotin compounds by headspace solid-phase microextraction–gas chromatography–pulsed flame-photometric detection (HS-SPME–GC–PFPD)

A method based on Headspace solid-phase microextraction (HS-SPME, with a 100 μm PDMS-fiber) in combination with gas-chromatography and pulsed flame-photometric detection (GC-PFPD) has been investigated for simultaneous determination of eight organotin compounds. Monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), monophenyltin (MPhT), and the semi-volatile diphenyltin (DPhT), triphenyltin (TPhT), monooctyltin (MOcT), and dioctyltin (DOcT) were determined after derivatization with sodium tetraethylborate. The conditions used for the extraction and preconcentration step were optimised by experimental design methodology. Tripropyltin (TPrT) and diheptyltin (DHepT) were used as internal standards for quantification of volatile and semi-volatile organotin compounds, respectively. The analytical precision (RSD) for ten successive injections of a standard mixture containing all the organic tin compounds ranged between 2 and 11%. The limits of detection for all the organotin compounds were sub ng (Sn) L⁻¹ in water and close to ng (Sn) kg⁻¹ in sediments. The accuracy of the method was evaluated by analysis of two certified reference material (CRM) sediment samples. The HS-SPME–GC–PFPD was then applied to the analysis of three harbour sediment samples. The results showed that headspace SPME is an attractive tool for analysis of organotin compounds in solid environmental matrices.     

Determination of butyltin compounds in surface sediments from the São Paulo State coast (Brazil) by gas chromatography-pulsed flame photometric detection

Occurrence and the effects of butyltin compounds (BTs) have been studied for some years, mainly in countries of the Northern Hemisphere. Due to widespread use of tributyltin compounds (TBTs) and considering their deleterious effects, it is necessary to conduct studies on its occurrence, especially in the marine environment because of its excessive use in coatings of ship hulls to prevent fouling. Moreover, it was important to extend the evaluation to areas where there is no current information about their occurrence. The present work reports the occurrence of BTs in marine sediments of S?o Paulo state, Brazil. Commercial and leisure harbor sampling sites were selected because these areas are potentially exposed to BTs from antifouling paints used on ship hulls. Analytical conditions for organotin analysis in marine sediments were optimized for GC with pulsed flame photometric detection. Detection limits ranged from 8A to 66.3 ng g(-1) using a 610-nm filter, and the linearity range was 20-500 ng g(-1). Concentration levels of BTs were highest in Santos harbor (360 ng g(-1) TBT in average) and Guarujá marina (670 ng g(-1) TBT in average), which seems to be related to intensive boat traffic. Lower levels of BTs were observed in Cananéia, where only fishing boats are present (50 ng g(-1) TBT in average).     

Imposex and organotin body burden in the dog‐whelk (Nucella lapillus L.) along the Portuguese coast

Nucella lapillus imposex—superimposition of male characters onto prosobranch (a subclass of gastropod molluscs) females—and organotin female body burden were surveyed on the Portuguese coast, from Vila Praia de Âncora (northern limit) to Praia da Luz (southern limit), at 17 sampling stations, between May and August 2003. The vas deferens sequence index (VDSI), the relative penis size index (RPSI), the percentage of females affected with imposex (%I) and the percentage of sterile females (%S) were used to assess the level of imposex at each site. VDSI, RPSI and %I were 0.20–4.04, 0.0–42.2% and 16.7–100.0%, respectively. Sterile females were found at stations 2 (6.2%), 5 (4.0%) and 7 (5.0%). Tributyltin (TBT) and dibutyltin (DBT) female body burdens were 23–138 and <10–62 ng Sn/g dry weight, respectively. TBT female body burden was significantly correlated with RPSI and VDSI [Spearman rank order linear correlation: RPSI vs TBT body burden (b.b.) r = 0.71, p < 0.01; VDSI vs logTBT body burden r = 0.71, p < 0.01]. Imposex and TBT b.b. were highest at sites located in the proximity of harbours, where TBT leaching from antifouling paints is more intense owing to the high concentration of ships and dockyard activities. Copyright © 2005 John Wiley & Sons, Ltd.     

Imposex and organotin contamination in Nassarius reticulatus (L.) along the Portuguese coast

Nassarius reticulatus (whelk) imposex levels and organotin body burden (b.b.) were surveyed along the Portuguese coast, from Vila Praia de Âncora (northern limit) to Lagos (southern limit), between May and August 2003. The percentage of females affected with imposex (%I), the relative penis length index (RPLI), the vas deferens sequence index (VDSI) and the degree of female oviduct convolution index (AOS) were used to assess the level of imposex at each site. These imposex indices were determined for 23 sampling stations throughout the coast and were in the range 0.0–100%, 0.0–90%, 0.0–5.0 and 0.0–1.3 respectively. Sterile females (i.e. females carrying aborted egg capsules inside the capsule gland) were found inside the harbours of Viana do Castelo (8.5%) and Aveiro (3.7%). Organotin compounds were assessed at 10 sampling sites spread along the coast. Tributyltin (TBT) b.b. in females varied between 39 and 1679 ng g^?1 (as tin) dry weight, and dibutyltin (DBT) and monobutyltin (MBT) varied in the ranges 23–1084 ng g^?1 (as tin) d and 18–939 ng g^?1 dry wt respectively. Among the butyltins, the major fraction corresponded to TBT (47.4%), followed by DBT (27.6%) and MBT (25.0%), which indicates recent TBT inputs. Triphenyltin (TPT) levels ranged from <5 to 21 ng g^?1 (as tin), and, when quantifiable, represented on average 10% of that of TBT. TPT was the dominant phenyltin and was detected in 60% of the sampling stations. The imposex was significantly correlated to ln (TBT) (Spearman r = 0.918, p < 0.001 for RPLI; r = 0.864, p < 0.001 for VDSI; r = 0.828, p < 0.01 for AOS). The higher levels of imposex and TBT contamination occurred inside or close to harbours, which we identified as ‘hotspots’ of pollution along the coast. Comparing the results obtained in the current work with those reported in a similar survey in 2000, imposex and TBT b.b. varied locally but did not reveal any global trend in the variation of TBT pollution along the Portuguese coast over the 3 year period. Copyright © 2005 John Wiley & Sons, Ltd.     

Contamination and biomethylation of organotin compounds in pearl/fish culture areas in Japan.

Uwakai of Japan is famous for pearl and yellowtail fish culture. Recently, pearl culture farming in that region has suffered from a low production of pearls. An illegal use of organotin antifouling paints on fishing nets was reported. In the line of pollution studies, thus, the present investigation was carried out to examine the contamination status and fate of organotin compounds. Totally, 23 water, 10 sediment and 8 pearl oyster tissue samples were analyzed for tributyltin (TBT), triphenyltin (TPT), and their breakdown products (di- and mono compounds) by gas chromatography combined with inductively coupled plasma mass spectrometry (GC/ICP-MS). The results show that the TBT concentrations in water, sediment and biota were in the range from 0.11 to 10.6 ng Sn l(-1), 0.35 to 2500 ng Sn g(-1), and 50.4 to 181 ng Sn g(-1), respectively. The values for sediment and biota are expressed on the dry-weight basis. Triphenyltin in water, sediment and biota were in the range from 0.009 to 0.108 ng l(-1), non-detect to 12.7 ng g(-1), and non-detect to 6.83 ng g(-1), respectively. Although the TBT concentration in seawater is below the tentative assessment level of 10 ng l(-1) set by the Japanese Environment Agency in 1992, it may cause endocrine disruption/other effects in aquatic organisms. Octyltin compounds (mono-, di- and trioctyltin) were also quantified in seawater and sediment. The detection of dibutyldimethyltin (DBDMT) and tributylmonomethyltin (TBMMT) in sediment (methylated butyltins comprised 2.8-31% of total butyltins), and TBMMT in seawater suggested that biomethylation of anthropogenic tributyltins is a significant transformation pathway in the coastal environment.     

Life‐cycle toxicity of dibutyltin to the sheepshead minnow (Cyprinodon variegatus) and implications of the ubiquitous tributyltin impurity in test material

Dibutyltin (DBT) is used in the plastics polymerization process as a catalyst in polyvinyl chloride (PVC) products and is the primary degradation product of tributyltin (TBT), an antifoulant in marine paint. DBT and other organotin compounds make their way into the environment through antifoulants, PVC processing plants, and PVC products maintained in water and water‐handling systems. A flow‐through saltwater life‐cycle toxicity test was conducted to determine the chronic effect of DBT to the sheepshead minnow (Cyprinodon variegatus Lacepede), an estuarine species. Embryos were monitored through hatch, maturation, growth, and reproduction in DBT concentrations of 158, 286, 453, 887, and 1510 µg l^?1. Progeny were monitored for survival as embryos and fry/juveniles, and growth for 30 days post‐isolation. Mean length of parental generation fish was significantly reduced on day 30 at DBT concentrations ≥887 µg l^?1, setting the lowest observable effect concentration (LOEC) at 887 µg l^?1 and the no observable effect concentration (NOEC) at 453 µg l^?1. Fecundity, as egg viability, was significantly reduced at the LOEC. Survival of parental and progeny generation embryos and mean length, wet weight and dry weight of progeny generation juveniles were not significantly affected at concentrations ≤LOEC. TBT, a toxic impurity in DBT reversibly produced in DBT by the process of comproportionation, was also monitored throughout this study. Comparing measured levels of TBT in this study with levels exerting toxic effects in an earlier TBT life‐cycle study with C. variegatus suggests biological responses in this study were likely due to the TBT impurity and not to DBT alone. Results indicate that TBT impurity as low as 0.1% may have a significant influence on the perceived toxicity of DBT and that spontaneous production of TBT in DBT may be the major source of biological toxicity of DBT. Copyright © 2003 John Wiley & Sons, Ltd.     

Contamination of outdoor settled dust by butyltins in Malta

The presence of compounds of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) was determined in outdoor settled dust collected from several sites on the island of Malta, mainly from flat rooftops of school buildings. The dust was separated into three size fractions with diameters (µm) > 250, 125–250 and < 125, and the two finer fractions were analysed for butyltins using extraction with glacial acetic acid followed by derivatization/solvent extraction with sodium tetraethylborate in the presence of iso‐octane and quantitation by gas chromatography with flame photometric detection. The presence of TBT, DBT and MBT was established in most of the samples and TBT concentrations varied from non‐detectable (<5 ng Sn g^?1) to highs of 15.5 and 18.7 µg Sn g^?1 in Senglea and Marsaxlokk. TBT was generally found at concentrations significantly higher than reported hitherto in house dust collected from European homes. The geographical distribution of total organotins in both dust fractions suggests that TBT originates mainly from antifouling marine paint residues which contaminate the urban environment when ships' hulls are sand‐ or hydro‐blasted during maintenance and repair at the drydocks facility in Grand Harbour. Other significant sources of TBT are located at Marsaxlokk fishing port and Wied i?‐?urrieq creek, both hosting sizeable communities of fishermen and leisure boating. The data also suggest that the municipal solid waste landfill at Maghtab is an inland source of butyltins. We suggest that dust containing harmful butyltins could possibly be ingested to expose humans to a risk which is probably of concern especially for young children living close to the hotspots of contamination. Copyright © 2007 John Wiley & Sons, Ltd.     

Effects of tin(IV) chloride and of organotin compounds on aquatic micro-organisms

The growth response of the alga Chlorella kessleri and the euglenoid Euglena gracilis has been studied as a model system to determine the effects of a tin salt (SnCl₄·5H₂O) and of some organotin (OT) derivatives, namely tetrabutyltin (TeBT), tributyltin (TBT) and tributyltin oxide (TBTO). Abiotic degradation was studied as well. Cells were exposed to a toxicity series (0–50 μg/mL⁻¹) for the four chemicals in seven-day bioassays. Both microorganisms are tolerant of the inorganic salt, but growth inhibition was significant for all OT compounds, and especially large for TBT and TBTO. Although C. kessleri and E. gracilis are known to be tolerant towards metals and organic chemicals, the present results show that both are sensitive to organotin compounds: the inhibition of the growth was greater for C. kessleri. © 1998 John Wiley & Sons, Ltd.     

Organotin contamination,imposex and androgen/oestrogen ratios in natural populations of Nassarius reticulatus along a ship density gradient

Levels of organotin body burden (expressed as tin), imposex and steroid hormones (testosterone, 17β‐oestradiol, testosterone glucuronide and sulfate conjugates) were investigated in natural populations of Nassarius reticulatus in the Ria de Aveiro (northwest Portugal) between 1997 and 1999. The tributyltin (TBT) whole body burden (b.b.) of females presented increasing gradients from the adjacent open coast (16–26 ng g^?1 dry weight (d.w.)) towards the ports inside the Ria de Aveiro (195–272 ng g^?1 d.w.). Triphenyltin b.b. was only detected at the most polluted port (22 ng g^?1 d.w.). Imposex also presented increasing values from the adjacent coast (vas deferens sequence index (VDSI): 0.0–0.5; relative penis length index (RPLI): 0.0–2.4; penis length index (PLI): 0.0–0.3 mm; percentage of affected females (%I): 0–30) towards the ports (VDSI: 3.8–4.8; RPLI: 51–80; PLI: 6.7–10.8 mm; %I: 100). The testosterone levels in females without imposex were always lower than in females with imposex, and the ratio of testosterone/17β‐oestradiol in females tended to increase with increasing imposex and organotin contamination. In spite of the large difference in the female testosterone and 17β‐oestradiol levels between summer and winter, related to the reproductive cycle, the spatial trend of the testosterone/17β‐oestradiol ratio was remarkably similar in shape and values in the two seasons. Imposex was significantly correlated with the TBT b.b. and the testosterone/17β‐oestradiol ratio in females. The testosterone conjugate levels did not show any clear pattern with the increasing values of imposex and TBT contamination. Copyright © 2005 John Wiley & Sons, Ltd.     

Occurrence of butyltin compounds in marine sediments and bivalves from three harbour areas (Saigon,Da Nang and Hai Phong) in Vietnam

A survey of organotin compounds comprising tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) in sediment and clam (Meretrix meretrix) was undertaken in Vietnam in 2003. Samples were collected from dry docks and cargo harbours in Ho Chi Minh (south), Da Nang (centre) and Hai Phong (north) cities. Measurable amounts of TBT, DBT and MBT were found in all samples. The total concentration of the butyltin compounds (ΣBTs) in sediment from shipyards and vessel repair yards (Nam Trieu, Song Cam, Lach Tray and Ba Son) were always higher than those measured in cargo ports (Hai Phong, Da Nang, and Sai Gon). The highest ΣBTs concentration (as tin: 122 ng g^?1 dry wt) was found in the sediment from Song Cam station, where seven shipyards are located. The lowest concentrations of ΣBTs occurred in sediments from the Da Nang and Hai Phong cargo ports (as tin: 21–22 ng g^?1 dry wt). This implies that the major source of BTs in the marine environment in Vietnam is from the shipbuilding activities. The ratio of TBT to Σ(MBT + DBT) in sediment was 0.67 ± 0.03 for all the sampling sites, indicating the recent use of TBT in Vietnam. For the clam (M. meretrix), the concentration of ΣBTs (as tin) varied in the range 11.2–60.1 ng g^?1 wet wt. There was a good correlation (R² = 0.85) between total organic matter‐normalized ΣBTs in sediment and hexane‐extractable organic matter‐normalized ΣBTs in clam soft tissue. The mean biota–sediment accumulation factors (organic carbon/lipid) for MBT, DBT and TBT in clam's soft tissue were found to be 1.83 ± 0.66, 1.44 ± 0.23 and 1.16 ± 0.47 respectively, indicating that sediment‐bound BTs might be an important source of contamination for the clam. Copyright © 2005 John Wiley & Sons, Ltd.     

Speciation of Organotin Compounds by Capillary Electrophoresis Coupled with Hydride Generation Atomic Fluorescence Spectrometry

Abstract

Capillary electrophoresis (CE) coupled with hydride generation atomic fluorescence spectrometry (HG‐AFS) was developed for the speciation analysis of organotin compounds. The four organotin cations of trimethyltin (TMT), monobutyltin (MBT), dibutyltin (DBT), and tributyltin (TBT) were completely separated by CE in a 50 cm×75 µm i.d. fused‐silica capillary at 15 kV and using a mixture of 50 mmol l^?1 H₃BO₃?50 mmol l^?1 Tris‐5% v/v methanol (pH 7.10) as electrolyte. 0.008 mmol l^?1 cetyltrimethylammonium bromide (CTAB) added to the electrolyte suppressed the adsorption of the organotin cations on the inner wall of capillary. The generated hydride species were detected on‐line with AFS. The precisions (RSD, n=5) were in the range of 1.7–3.1% for migration time and 3.8–4.7% for peak area response for the four organotin species. The detection limits ranged from 1–10 µmol l^?1 (as Sn).     

Contamination by butyltin compounds in harbour porpoise (Phocoena phocoena) from the Black Sea

Concentrations of butyltin compounds (BTs) were determined in harbour porpoise (Phocoena phocoena) collected from the Turkish coastal waters of the Black Sea. Total butyltin compounds (∑ BTs) in the liver were in the range of 89–219 ng/g on a wet weight basis. The dibutyltin (DBT) residues were higher than those of tributyltin (TBT), suggesting the degradation of TBT to DBT in the liver and the metabolic capacity comparable to other marine mammals. Any sex difference and age-dependent accumulation of BTs residues were not found in harbour porpoises, but residue levels increased until maturity and then remained constant. When compared with other marine mammals, the present results indicate that the Black Sea is also contaminated with butyltin compounds, but to a lesser degree than coastal waters of developed nations. The biomagnification factor in harbour porpoises was 0.8, which was comparable with pinnipeds and lower than cetaceans. Received: 23 December 1996 / Revised: 15 April 1997 / Accepted: 16 April 1997     

Accumulation and toxic effect of organometallic compounds on algae

This paper reports toxic effects and bioaccumulation factors of organometallic compounds, mainly organotin species, on algae. We selected two species of microalgae as test algae: one was Scenedesmus obliquus as a representative of fresh-water algae, the other Dunaliella salina and Dunaliella viridis, to represent commonly mixed algae which exist abundantly in Tianjin Harbor, People's Republic of China. For comparison, Chlorella vulgaris was also used in this study. The toxic effect of ten organometallic compounds on the freshwater alga, S. obliquus, was investigated. The ten compounds were (as chlorides) tributyltin (TBT); triphenyltin (TPT); trimethyltin (TMT); dibutyltin (DBT); diphenyltin (DPT); dimethyltin (DMT); trimethyl-lead acetate (TML); dimethyl-arsine (DMA) and two new mixed-alkyltin pesticides, dicyclohexylmethylitin acetate (Cy₂MTA) and dicyclohexylmethyltin isobutyrate (Cy₂MTB). The order of toxicity of these compounds in fresh-water algae, S. obliquus, was TBT>TPT>DBT> Cy₂MTA=TML> Cy₂MTB>DPT>TMT>DMA>DMT, according to 96 h EC₅₀ values attained. The ten toxicants were divided into three groups according to the sequence of their toxicities; (a) TBT, TPT; (b) DBT, Cy₂MTA, TML, Cy₂MTB; (c) DPT, TMT, DMA, DMT. In each group the EC₅₀ values of each compound were quite similar. The difference of EC₅₀ values between two vicinal groups was approximately one order of magnitude. The bioconcentration factor (BCF) of TBT and TPT compared with water in the freshwater alga S. obliquus was >3.32 × 10⁵ and 1.14 × 10⁵, respectively. The BCF of the marine mixed algae was >3.48 × 10⁵. The marine microalga, Chlorella vulgaris, was adaptable to TBT at lower concentration. TBT at high concentration only inhibited the growth of S. obliquus, but it could cause chlorosis anddisintegration of D. salina and D. viridis. Resistance to toxicity of algae against TBT appears in order as follows: C. vulgaris>S. obliquus>D. salina and D. viridis. TBT was metabolized by algae to a less toxic product, DBT. The existence of algal cells accelerated the concentration reduction of TBT. The toxic mechanism of TBT was also studied.     

Contamination by butyltin compounds in harbour porpoise (Phocoena phocoena) from the Black Sea

Concentrations of butyltin compounds (BTs) were determined in harbour porpoise (Phocoena phocoena) collected from the Turkish coastal waters of the Black Sea. Total butyltin compounds (∑ BTs) in the liver were in the range of 89–219 ng/g on a wet weight basis. The dibutyltin (DBT) residues were higher than those of tributyltin (TBT), suggesting the degradation of TBT to DBT in the liver and the metabolic capacity comparable to other marine mammals. Any sex difference and age-dependent accumulation of BTs residues were not found in harbour porpoises, but residue levels increased until maturity and then remained constant. When compared with other marine mammals, the present results indicate that the Black Sea is also contaminated with butyltin compounds, but to a lesser degree than coastal waters of developed nations. The biomagnification factor in harbour porpoises was 0.8, which was comparable with pinnipeds and lower than cetaceans. Received: 23 December 1996 / Revised: 15 April 1997 / Accepted: 16 April 1997     

Soils of Azores islands: elemental characterization with an emphasis on rare-earth elements

This work addresses the chemical features of topsoils from Pico, São Jorge and São Miguel islands (Azores, Portugal), resulting from the weathering of more or less recent volcanic materials, namely pyroclastic debris, scoriae and basaltic rocks. The fractions under 64 μm of the surface-soil samples (0–10 cm) were put through k ₀-standardized, instrumental neutron activation analysis (k ₀-INAA), and their contents in 29 chemical elements were determined. Overall, the results show the chemical composition in the top horizon of soils to be correlated with the type of initial material, as well as with the age of formation of the island. The more relevant differences between the surveyed islands are: (1) a positive Ce anomaly in soils from São Miguel, most probably due to the higher age of that island; and (2) a fractionation between heavy and light rare-earth elements (REEs) in São Miguel, not found in the younger Pico and São Jorge. Other than the islands’ age, terrain altitude seems another relevant factor in differentiating the topsoils’ composition.     

Soils of Sao Domingos mine: REE chemical characterization

This work addresses the chemical features of topsoils from São Domingos mine, Portugal, an abandoned mining area since middle of twentieth century. The fractions below 1 mm of the surface-soil samples (0–15 cm) were measured by k₀-standardized, instrumental neutron activation analysis in order to determine the levels of rare earth element concentrations in comparison to control soils. A fractionation between the heavy and light rare-earth elements (REEs) occurred, with the latter enriched relatively to the first ones. The REEs pattern is similar in all sites with higher concentrations in the mine area as compared to the control site. The ratios between REEs are conventional for three subsamples but slightly diverge for the other sites. The REEs pattern is similar to one of the volcanic islands still with activity as Sao Miguel in Azores, Portugal, and similar to the one of an industrial area containing coal power plant and refinery.