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     

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.     

Modulation of the F1FO‐ATPase function by butyltin compounds

Among butyltin compounds, tributyltin (TBT), widely exploited in the past in antifouling paints for its biocidal properties, is long known as one of the most harmful sea contaminants. Among the ascertained and universal toxicity mechanisms, TBT targeting F₁F_O‐ATPase and thus impairing cell bioenergetics, is here reviewed. While TBT effects on F₁F_O‐ATPase have been investigated for decades, the possible impact of the derivatives dibutyltin (DBT) and monobutyltin (MBT), produced by abiotic and/or biotic dealkylation of TBT and usually considered far less toxic, have been poorly explored up until now. Butyltin effects on F₁F_O‐ATPase and their underlying action mechanism seem to be tightly structure dependent. Butyltins are membrane‐active toxicants. Owing to its more pronounced lipophilicity TBT targets the transmembrane F_O sector, blocks ionic translocation and causes a dose‐dependent loss of sensitivity to F_O inhibitors such as oligomycin and N,N′‐dicyclohexylcarbodiimide. DBT strongly inhibits F₁F_O‐ATPase activity by competing with the Mg⁺² cofactor in the F₁ catalytic site but is ineffective on the enzyme sensitivity to F_O inhibitors. MBT is apparently ineffective. The possible contribution of DBT to the overall butyltin toxicity on membrane systems may not be neglectable since usually TBT coexists with its derivatives in organotin‐exposed animal tissues. Copyright © 2013 John Wiley & Sons, Ltd.     

Speciation of butyltin compounds by on-line HPLC-ETAA of tropolone complexes in environmental samples

Tropolone (Trop) forms in solution stable complexes with monobutyltin (MBT Trop₂) and dibutyltin (DBT Trop). This property has been used to develop a separation procedure of butyltin compounds by liquid chromatography on cyanopropyl-bonded silica columns with a solution of tropolone in toluene as eluent. Tin-specific detection by on-line ETAA allowed the development of a simple procedure suitable for the determination of tributyltin and dibutyltin in water and sediment samples.     

Instrumental neutron activation analysis of extractable organohalogens in marine mammal,harbour porpoise (<Emphasis Type="Italic">Phocoena phocoena</Emphasis>) and its feed,Atlantic herring (<Emphasis Type="Italic">Clupea harengus</Emphasis>), from the Baltic Sea

Instrumental neutron activation analysis (INAA) was conducted for the analysis of extractable organohalogens (EOX) in the blubber samples of harbour porpoise (Phocoena phocoena) and whole body samples of Atlantic herring (Clupea harengus) from the Baltic Sea. The concentration order of EOX was: extractable organochlorine (EOCl) > extractable organobromine (EOBr) > extractable organoiodine (EOI). As the results of investigation into the biomagnification properties of EOX, EOBr in low molecular weight fraction was the highest among the organic halogens investigated, suggesting the presence of high persistent organic bromine compounds in the marine environment, and accumulation through food chains.     

Simultaneous determination of butyltin and phenyltin compounds in oysters by capillary gas chromatography

A method is described for the simultaneous determination of butyl- and phenyltin compounds in oyster samples. The organotin compounds were extracted (as chlorides) from oyster homogenates with hydrochloric acid and benzene in the presence of 0.05% tropolone. These compounds were converted into pentyl derivatives with pentyl Grignard reagent and then analysed by capillary gas chromatography with a flame photometric detector equipped with a 393-nm filter. The recoveries of six organotin compounds added to oyster samples ranged from 71 to 74%. The detection limits of butyl- and phenyltin compounds were in the 5-9 pg range as tin. We detected significant amounts of three organotin compounds (di- and tributyltin and triphenyltin) in oyster samples.     

Accumulation of butyltin compounds in dolphins stranded along the Mediterranean coasts

Concentrations of tributyltin (TBT) and its degradation products, monobutyltin (MBT) and dibutyltin (DBT), were determined in the liver and kidney of striped dolphins ( Stenella coeruleoalba), bottlenose dolphins ( Tursiops truncatus) and in a fetus of the common dolphin (Delphinus delphi) found stranded along the western Italian and Greek coasts in the period 1992–1994. Butyltin (BT) compounds were detected in almost all the samples analyzed and were higher in the kidney than in the liver. Total BT concentrations were 0.78–8.05 μg g⁻¹ wet wt in kidney and 0.015–1.02 μg g⁻¹ wet wt in liver of S. coeruloealba. Bottlenose dolphins had lower BT concentrations than striped dolphins. Although only one fetal sample was analyzed, it showed the highest BT concentrations of all. Unlike BT concentrations in the other adult dolphins, in the pregnant dolphin they were higher in the liver (4.35 μg g⁻¹ wet wt), suggesting that BTs are transferred from mother to fetus. No significant differences in BT concentrations were found between sexes. Of the breakdown products, DBT was predominant in most liver samples and MBT was more abundant in kidney. Although BT concentrations are known to be found in cetaceans inhabiting waters of developed countries, our observations strongly suggest that concentrations found in S. coeruleoalba were either similar to or higher than those reported for other Stenella species collected from coastal areas close to harbors or marinas. Copyright © 2000 John Wiley & Sons, Ltd.     

Multivariate optimization approach for the analysis of butyltin compounds in mussel tissues by gas chromatography-mass spectrometry

The derivatization with NaBEt(4) for the determination of butyltin compounds in mussel tissues (Mytilus galloprovincialis) by GC-MS was optimized using a central composite design. The effects of NaBEt(4) concentration, pH and acetate buffer concentration on the derivatization efficiency were considered. Solid-phase extraction with Florisil cartridges was performed, demonstrating that the clean-up drastically reduces the background and improves the sensitivity. The good accuracy of the method was verified on a certified reference material (ERM 477); the figures of merit for all the three analytes, evaluated under optimum conditions, were satisfactory. The optimized derivatization procedure was applied to the determination of the analytes in mussels exposed to tributyltin (TBT). All considered tissues showed considerable accumulation of TBT, especially gills.     

Matrix effects in the determination of butyltin compounds in environmental samples by GC AA after hydride generation

Experiments for the determination of mono-, di and tri-butyltin (MBT, DBT and TBT) by hydride generation/gas chromatography/atomic absorption spectrometry in various matrices (sediment, suspended matter, mussel, algae and water) have revealed that poor butyltin recoveries are obtained in sediments displaying high sulphur and hydrocarbon contents; very poor recoveries were also observed for TBT in sediments with high chlorophyll pigment contents as well as in algal samples. It was however not clear whether the hydride generatin was inhibited by these infering compounds, as was previously assumed in the case of hydrocarbons, or whether interferences affected the atomization rate. Further studies were performed to solve this problem in order to validate this method in the case of analyses of, for example, oil-contaminated sediment and algae. This paper presents the results obtained. It is concluded here that the poor recoveries were due to an inhibition of hydride generation rather than to interference at the atomization stage.     

Isotope dilution GC-MS routine method for the determination of butyltin compounds in water

A standard GC-MS instrument with electron impact ionisation has been used to develop a fast, simple and reliable method for the simultaneous determination of monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT) in water samples. Isotope dilution analysis (IDA) is used for the determination of species, taking advantage of a commercially available spike solution containing a mixture of MBT, DBT and TBT enriched in ¹¹⁹Sn. Method detection limits for 100-mL samples were between 0.18 and 0.25 ng L⁻¹ for the three butyltin compounds with typical RSD between 2 and 4% at levels between 100 and 10 ng L⁻¹, respectively. Recovery of tin species in spiked samples (natural water, wastewater and seawater) was quantitative. The stability of butyltin compounds in collected seawater samples was also studied. The addition of a 1% (v/v) glacial acetic acid preserved tin species in the samples for at least 5 days at room temperature. The IDA method was finally implemented in a routine testing laboratory and it was subsequently accredited by the Spanish National Accreditation Body according to the requirements of UNE-EN ISO/IEC 17025.     

Radionuclide uptake in red macroalgae from the Bulgarian Black Sea coast

Summary Technogenic and natural radionuclide content in red macroalgae (Ceramium rubrum, Corallina officinalisand Callithamnion corymbosum) from the Bulgarian Black Sea coast, collected in the period 1992-2003, was studied by low-level gamma-spectrometry. The data show that the nuclide concentrations depend on macroalgae species and coast locations. The highest nuclide content was measured in Ceramium rubrumspecies. The ¹³⁷Cs mean value is 9.8 Bq/kg, 19.6 Bq/kg for ²²⁶Ra and 17 Bq/kg for ²¹⁰Pb. The radionuclide pollution is considerably small due to the absence of nuclear facilities along the Bulgarian Black Sea coast.     

南海软珊瑚Sarcophyton molle化学成分的研究(一)

从中国南海软珊瑚（Sarcophytonmolle）中分离到三个含氮化合物，其结构经紫外光谱（UV）、红外光谱（IR）、质谱（MS）和核磁共振（1HNMR、13CNMR）分析分别确定为神经酰胺Sinumeramide（Ⅰ），胸腺嘧啶（Ⅱ）和脱氧尿核嘧啶苷（Ⅲ）．本文是首次报导该种属软珊瑚的化学成分。     

Quantitative analysis of sea-bed sediments from Eastern Black Sea by EDXRF spectrometry

Sea-bed sediments from Eastern Black Sea have been analyzed for their Fe, Ba and Sr contents using the methods of standard addition and energy dispersive X-ray fluorescence (EDXRF). Samples were prepared from powder sifted by a 200 mesh sieve. An annular 100 mCi²⁴¹Am radioactive source emitting 59.543 keV photons was used for excitation and a Ge(Li) detector, which has a 190 eV FWHM for 5.9 keV photons was used for intensity measurements. 2048 channels of the MCA are employed for 20 or 30 min. Dried and ground sea-bed sediments are found to contain 2.95–7.50% Fe, 0.032–0.268% Ba and about 73–273 ppm Sr. These results agree with those obtained via atomic absorption methods.     

The quantitation of butyltin and cyclohexyltin compounds in the marine environment of British Columbia

A HPLC/GF AA procedure based on the use of C-18 columns is described for the quantitation of butyltin species in marine samples. When a mass spectrometer was used as detector (HPLC MS), evidence was obtained for the presence of other tin compounds in the samples. Extracts of samples were treated with CH₃MgBr and examined by using GC MS; the presence of Bu_nSnMe_4?n (n = 3–1, Bu = butyl) and Cy_nSnMe_4?n (n = 3,2, Cy = cyclohexyl) was confirmed in the derivatized seawater, bivalve flesh, and bivalve shell samples. Quantitative data are given for butyl- and cyclohexyl-tin species in seawater and the surface microlayer, and oyster flesh.     

Simultaneous speciation of butyltin and phenyltin compounds in the waters of south-west Spain.

An analytical method for the simultaneous speciation of butylin and phenyltin compounds has been applied to a study of the water quality in six locations (rivers and sea) in South West Spain. It was not intended to provide a comprehensive survey of the area but to establish what the maximum levels might be for a subsequent and more detailed study. Phenyltin species were not found in any sample, however tributyltin was present (100-400 ng l-1) in the Cadiz Bay samples, which suggests that the biological water quality may sometimes be depressed. Wherever tributyltin was present, dibutyltin and monobutyltin occurred, possibly, as a result of a degradation process.     

Some investigations of sea sands from the Black Sea coastline

Alpha to spontaneous fission branching ratios of heavy actinides such as²³⁸Pu and²⁴⁰Pu in solution have been determined by solid state nuclear track detectors (SSNTDs). The detectors used in the present studies are LR-115, CR-39 (DOP), Lexan polycarbonate and Tuffak polycarbonate. Before using Tuffak polycarbonate, a detailed and systematic study on the registration and chemical etching characteristics of fission fragment tracks in this detector was also carried out. The experimentally measured values of alpha to spontaneous fission ratios by this method are found to agree well with the expected values.     

Radioactive accumulation in alga samples from Romanian Black Sea coast

The natural and artificial radioactivity of the brown algaCystoseira barbata samples collected on the Romanian Black Sea coast in 1996 is reported. The results on¹³⁷Cs were obtained through gamma-spectrometry, on⁹⁰Sr by beta-counting of the⁹⁰Y oxalate precipitated after strontium separation, on²²⁶Ra by the emanation method, while the concentrations of U, Th, Pu and Am isotopes were obtained through radiochemical separations using tracers followed by alpha-spectrometry counting of the stainless steel discs after electrodeposition. These results add further evidence thatCystoseira barbata may be used as a bioindicator for radioactive contamination of the coastal waters.     

Applicability of solid-phase microextraction combined with gas chromatography atomic emission detection (GC-MIP AED) for the determination of butyltin compounds in sediment samples

The performance of solid-phase microextraction (SPME) applied to the determination of butyltin compounds in sediment samples is systematically evaluated. Matrix effects and influence of blank signals on the detection limits of the method are studied in detail. The interval of linear response is also evaluated in order to assess the applicability of the method to sediments polluted with butyltin compounds over a large range of concentrations. Advantages and drawbacks of including an SPME step, instead of the classic liquid–liquid extraction of the derivatized analytes, in the determination of butyltin compounds in sediment samples are considered in terms of achieved detection limits and experimental effort. Analytes were extracted from the samples by sonication using glacial acetic acid. An aliquot of the centrifuged extract was placed on a vial where compounds were ethylated and concentrated on a PDMS fiber using the headspace mode. Determinations were carried out using GC-MIP AED.     

Speciation of butyltin compounds in marine sediments by preconcentration on C60 and gas chromatography-mass spectrometry

A new method for the speciation of butyltin compounds by solid phase extraction and direct injection using gas chromatography-mass spectrometry (GC/MS) is described. The compounds were complexed with sodium diethyldithiocarbamate and retained on a C60 sorbent column. The neutral chelates of butyltin compounds were eluted with ethyl acetate containing NaBPr4 as derivatising reagent. The main analytical figures of merit of the proposed method for 10 ml of sample are: linear range 0.2-35 ng/g expressed as Sn; limits of detection, 0.07, 0.09 and 0.10 ng/g as Sn for monobutyltin, dibutyltin and tributyltin, respectively. No interferences from metal ions such as Zn2+, Fe3+, Sb3t, Pb2+, Ni2+ and Mn2+ were observed in the determination of organotin compounds. The validation of method was performed out by the analysis of a standard reference sediment (CRM 462). The method was also applied to the determination of butyltin compounds in marine sediment samples.