Organotins (TBT and DBT) in water, sediments, and gastropods of the southern Venice lagoon (Italy)

The release of tributyltin (TBT) from maritime traffic represents one of the main problems of direct, diffuse, and continued contamination of the marine environment. In the present survey, the concentrations of TBT and dibultytin (DBT) in brackish waters, sediments, and the gastropods Nassarius nitidus were evaluated in order to estimate the contamination of the southern part of the Venice lagoon. TBT and DBT were determined by GC-MS/MS. Recent contamination of TBT was found in brackish waters near marinas, whereas the highest concentrations of TBT and DBT were observed in surface sediments at dockyards and harbours. High content of organotin in the gastropods sampled near the dockyards, harbours, and marinas showed a mobilisation from the sediments through the food web. The present study allowed assessment of whether, despite the ban on the use of TBT paints, waters, sediments, and biota were still being contaminated by organotin compounds in the southern Venice lagoon.     

Effects of tributyltin (TBT) on the seagrass Ruppia maritima

The effects of tributyltin (TBT) on the seagrass Ruppia maritima were studied in two growth experiments. Plants were sampled at stations in Odense Fjord and Lunkebugten, Denmark, and replanted in reference sediment without TBT, reference sediment spiked with TBT, and in impacted sediment sampled in the highly TBT contaminated (7-57 microg kg (-1) dw) Odense Fjord. Plant performance was studied at weekly intervals for 3-4 weeks, by measuring net photosynthetic activity, respiration, relative growth rate (RGR) and number of leaves. Net photosynthetic activity in plants from spiked and impacted sediment was reduced by up to 60% relative to reference plants. Respiration both increased and decreased in response to TBT exposure, while RGR was generally lower in plants from contaminated sediments (reduced by 8-25%). The effects of spiked and impacted sediment differed between the experiments, which could be partly explained by the bioavailability of TBT in the two treatments, but also by adaptation of the plants from Odense Fjord to TBT. Measurements of enhanced TBT concentrations in the sediments in Odense Fjord suggest an impact of TBT on R. maritima is possible under in situ conditions.     

Adsorption of tributyltin by tributyltin resistant marine Pseudoalteromonas sp. cells

The isolate, Pesudoalteromonas sp. TBT1, could grow to overcome the toxicity of tributyltin chloride (TBTCl) up to 30 μM in the absence of Cl⁻ in the medium until the cells reached an exponential phase of growth. The viability, however, was reduced after the cells reached a stationary phase. The degradation products, such as dibutyltin (DBT) and monobutyltin (MBT), were not detected in the growth medium, indicating that the isolate has no ability to degrade TBT into less toxic DBT and MBT. Up to about 10^7.5 TBT molecules were adsorbed by a single cell. The observation of morphological changes with an electron microscope showed that the cell surface became wrinkled after exposure to the lethal concentration of 10 mM TBTCl. These results indicate that the resistance of the isolate toward the toxicity of TBTCl is not related to the unique cell surface, which seems to play an important role in preventing the diffusion of TBTCl into the cytoplasm.     

Imposex levels and concentrations of organotin compounds (TBT and its metabolites) in Nassarius nitidus from the Lagoon of Venice

Specimens of Nassarius nitidus were collected in seven stations of the Venice Lagoon to assess the levels of tributyltin (TBT) and its metabolites monobutyltin and dibutyltin in the tissues and monitor their effect on organisms, in particular the phenomenon of imposex (superimposition of male sexual characteristics on females). The following values of population indices were found: vas deferens sequence: 1.2 ± 0.7–4.0 ± 0.5; relative penis length: 6–47%. The least impacted station was situated in the northern part of the Lagoon, where females without imposex were found and Butyltin (BuTs) concentrations in the organisms (average sum of BuTs = 43 ± 14 ng Sn g⁻¹ w.) were significantly lower than in the other stations (range of average sum of BuTs: 101 ± 22–217 ± 27 ng Sn g⁻¹ d.w.). Population indices were found to be related to the TBT content in the tissues. In particular VDSI had a significant logarithmic correlation: r = 0.95, n = 8, p < 0.05.     

Biomonitoring of TBT contamination and imposex incidence along 4700 km of Argentinean shoreline (SW Atlantic: From 38S to 54S)

The imposex incidence and TBT pollution were investigated along 4,700 km of Argentinean coast, including city harbors and proximal zones without marine traffic. We analyzed 1805 individuals from 12 gastropod species, including families Volutidae, Muricidae, Nassariidea, Calyptraidae, Marginellidae, and Buccinidae, and found the imposex phenomenon for the first time in six species. In high marine traffic zones, TBT pollution was registered and the percentage of imposex was high, while these occurrences were null in areas without boat traffic. The species that best reflect the degree of imposex were those inhabiting sandy/muddy or mixed bottoms. TBT determination and imposex incidence indicate that pollution was focused only in ports with high marine traffic or in areas where ship hulls are painted. This is the first report of an imposex-sediment approach to evaluate organotin contamination along the coast of a South American country.     

Removal of Selenium by Adsorption onto Granular Activated Carbon (GAC) and Powdered Activated Carbon (PAC)

The present work involves the study of Se(IV) adsorption onto granular activated carbon (GAC) and powdered activated carbon (PAC). The adsorbents are coated with ferric chloride solution for the effective removal of selenium. The physico-chemical characterization of the adsorbents is carried out using standard methods, e. g., proximate analysis, scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FTIR), thermo-gravimetric (TGA) and differential thermal analysis (DTA), etc. The FTIR spectra of the GAC and PAC indicate the presence of various types of functional groups, e. g., free and hydrogen bonded OH groups, silanol groups (Si-OH), alkenes, and CO group stretching from aldehydes and ketones on the surface of adsorbents. Batch experiments are carried out to determine the effect of various factors such as adsorbent dose (w), initial pH, contact time (t), and temperature (T) on the adsorption process. The optimum GAC and PAC dosage is found to be 10 g/L and 8 g/L, respectively, for Se(IV) removal with C₀ = 100 mg/L. The percent removal of Se(IV) increases with increasing adsorbent concentration, while removal per unit weight of adsorbent increases with decreasing adsorbent concentration. Se(IV) adsorption onto both the GAC and PAC adsorbents is high at low pH values, and decreases with increased initial pH. The results obtained are analyzed by various kinetic models. The parameters of pseudo-first order, pseudo-second order kinetics, and Weber-Morris intra particle kinetics are determined. It is seen that the sorption kinetics of Se(IV) onto GAC and PAC can be best represented by the pseudo-second order kinetic model.     

Assessment of TBT and organic booster biocide contamination in seawater from coastal areas of South Korea

Seawater samples from major enclosed bays, fishing ports, and harbors of Korea were analyzed to determine levels of tributyltin (TBT) and booster biocides, which are antifouling agents used as alternatives to TBT. TBT levels were in the range of not detected (nd) to 23.9 ng Sn/L. Diuron and Irgarol 1051, at concentration ranges of 35–1360 ng/L and nd to 14 ng/L, respectively, were the most common alternative biocides present in seawater, with the highest concentrations detected in fishing ports. Hot spots were identified where TBT levels exceeded environmental quality targets even 6 years after a total ban on its use in Korea. Diuron exceeded the UK environmental quality standard (EQS) value in 73% of the fishing port samples, 64% of the major bays, and 42% of the harbors. Irgarol 1051 levels were marginally below the Dutch and UK EQS values at all sites.     

Dye Removal from Colored Textile Wastewater by Poly(propylene imine) Dendrimer: Operational Parameters and Isotherm Studies

This paper deals with the removal of textile dyes from aqueous solutions by poly(propylene imine) dendrimer (PPI). Direct red 80 (DR80), Acid Green 25 (AG25), Acid Blue 7 (AB7), and Direct Red 23 (DR23) were used as model dyes. The effects of operational parameters on dye removal such as dendrimer concentration, dye concentration, salt (inorganic anions), and pH have been studied at 25°C. The Langmuir and Freundlich isotherm models were investigated. In addition, dye desorption of dendrimer was studied. The results indicated that acidic pH supported the adsorption of dyes by dendrimer. Furthermore studies of dye concentration and salt effects exhibited that dye removal percentage by dendrimer was decreased. It was found that the isotherm data of DR80, AG25, and DR23 followed Langmuir isotherm and isotherm data of AB7 followed Freundlich isotherm models. Desorption tests showed that maximum dye releasing of 76.5% for DR80, 84.5% for AG25, 87% for AB7, and 93% for DR23 were achieved in aqueous solution at pH 12. Based on the data of present study, one could conclude that the dendrimer being an environmentally friendly adsorbent with relatively large adsorption capacity might be a suitable alternative for elimination of dyes from colored textile wastewater.     

Re-colonisation and recovery of populations of dogwhelks Nucella lapillus (L.) on shores formerly subject to severe TBT contamination

Dogwhelks Nucella lapillus became locally extinct on some shores adjacent to areas of high shipping/boating activity during the period of high tributyltin (TBT) contamination in the 1980s and early 1990s. However, the species has now re-colonised sites at which extinction occurred on the Isle of Cumbrae, the northeast coast of England, the Shetland Isles and southwest England. There have also been substantial declines in the severity of imposex on adjacent shores where the species has persisted during this period. Re-colonisation and recovery can be attributed to two measures: regulations prohibiting the use of TBT-based paints on vessels < 25 m in length and the development of slow-releasing, self-polishing copolymer paints. Nevertheless, the International Maritime Organisation has now imposed a total ban on the use of TBT-based paints as antifoulants. This is almost certain to result in the use of paints containing alternative biocides and there is widespread concern that there is relatively little information on which to assess their likely environmental impacts. They could cause substantial environmental damage.     

Management of exogenous threats to Antarctica and the sub-Antarctic Islands: balancing risks from TBT and non-indigenous marine organisms

The discovery of high levels of tributyltin compounds in Antarctic marine sediments has prompted managers to consider the banning of such substances in this region. We propose that the banning of antifouling coatings may result in an increase in the risk of non-indigenous species invasions. Our studies show that un-treated vessels carry a more diverse community of fouling organisms than treated hulls on which fouling is restricted to specific untreated niches. Up to 40% of the species recruited to the hulls of Southern Ocean vessels are species with invasive histories. Viable fouling assemblages can survive prolonged voyages to high-latitude coastlines, yet passage through sea-ice may remove fouling communities due to mechanical abrasion reducing the hazard of introductions to ice-bound coastlines. The banning of antifouling compounds may be of particular concern for the ice-free sub-Antarctic islands which represent a common anchorage point for vessels on-route to Antarctica.     

Use of Pistachio Shells as an Adsorbent for the Removal of Zinc(II) Ion

In this study, the removal of zinc(II) ion from an aqueous solution by pistachio shells (PS) is investigated. The dynamic behavior of the adsorption is examined on the effects of pH, adsorbent dosage, and contact time. The adsorption rates are determined quantitatively and simulated by the Lagergren first order, pseudo‐second order, Elovich, and intra‐particle diffusion kinetic models. The adsorption kinetic models are also tested for validity. The thermodynamic parameters, which are also deduced from adsorption experiments, are very useful in elucidating the nature of adsorption. The experimental results reveal that the optimum pH value and the contact time for the adsorption of Zn²⁺ onto PS are found as 6 and 10 min, respectively. According to these parameters, adsorption process follows the pseudo‐second order kinetic model with high correlation coefficients (R² = 0.999). The obtained results demonstrate that PS is a reasonably effective adsorbent for the removal of Zn²⁺ from aqueous leachate of hazardous waste.     

Adsorption Kinetic and Equilibrium Studies on Removal of Lead(II) onto Glutamic Acid/Sepiolite

In this study, a modified method was used to increase the adsorption of lead ions from aqueous solutions by using modified clay mineral on the laboratory scale. Adsorption experiments have been carried out on the use of both thermal activated sepiolite (TAS) and their glutamate/sepiolite modification (GS) as adsorbents. The experimental data was analyzed using adsorption kinetic models (pseudo first‐ and second‐order equations). The pseudo second‐order kinetic model fitted well to the kinetic data (R² ≥ 0.99). Then, the Freundlich and Langmuir models were applied to describe the uptake of Pb(II) on GS and the Langmuir isotherm model agrees well with the equilibrium experimental data (R² ≥ 0.97). The maximum adsorption capacity was observed to be 128.205 mg/g by GS according to the Langmuir equation. Desorption efficiency of the GS was studied by the batch method using EDTA, HCl, and HNO₃ solutions. Desorption of 69.18, 74.55, and 80% of Pb(II) from GS was achieved with 0.1 M EDTA, 0.1 M HCl, and 0.1 M HNO₃ solutions, respectively. FTIR analysis suggests the importance of functional groups such as amino, hydroxyl, and carboxyl during Pb(II) removal. SEM observations demonstrated that an important interaction at the lead‐modified sepiolite interface occurred during the adsorption process. In addition, the thermodynamic constants was calculated that the values of the Gibbs free energy (ΔG*), enthalpy (ΔH*), and entropy (ΔS*) of modification were 86.79 kJ/mol, ?18.91 kJ/mol, and ?354.70 J/mol/K, respectively. The negative value of ΔH* shows exothermic nature of adsorption.     

A review and assessment of tributyltin contamination in the North Sea,based on surveys of butyltin tissue burdens and imposex/intersex in four species of neogastropods

It is evident from measures of butyltin tissue burdens and imposex or intersex in neogastropods that tributyltin (TBT) contamination of coastal waters and open parts of the North Sea is now low. It has been declining for at least the past decade. This is probably due to two measures. First, regulations prohibiting the use of TBT-based paints on small boats and fish farms have reduced inputs of TBT from these sources so that they are now negligible (except possibly where the regulations are flaunted). Second, there is evidence from sites, where commercial vessels are the sole source of TBT, that the adoption of TBT SPC paints has been effective in reducing environmental levels of these contaminants. However, poor dockyard practices, allowing TBT-contaminated wastes, including paint flakes, to accumulate in sediments have left a legacy of hot-spots of contamination in some ports. The impact is localised so that TBT contamination is low in coastal areas immediately adjacent to ports.     

Spatial and temporal changes of TBT pollution along the Portuguese coast: inefficacy of the EEC directive 89/677

Nucella lapillus imposex (superimposition of male characters onto prosobranch females) and organotin body burden were surveyed in the Portuguese coast in 1997 and 2000. Time comparisons of the available data on Nucella lapillus imposex in the Portuguese coast indicate a global increase of TBT pollution in recent years, revealing the inefficacy of the 1993 legislation that bans the use of TBT paints on small boats (<25 m). The absence or scarcity of the species inside harbours, which are the most polluted sites in Portugal, is probably a consequence of extinction due to female sterilisation by TBT.     

Magnetic characteristics of sediment grains concurrently contaminated with TBT and metals near a shipyard in Busan,Korea

Bottom sediments near shipyards are often susceptible to receiving accidental spills of TBT and metals or their degradation products from hull scraping of antifouling system paints applied prior to 2008, when the AFS Convention 2001 was not in force. We investigated TBT and metal contamination of sediments near the shipyards of a small marina located in Busan, Korea and found that they were highly contaminated with TBT, Cu, and Zn. To better understand the environmental impacts and to make an optimal remediation plan, we characterized individual antifouling fragments in terms of metal and TBT contents, magnetic properties, and grain-size. Coarse-sized individual antifouling fragments exhibited simultaneously high levels of TBT, metals and high magnetic susceptibility, and appeared to be a major source of pollution in the sediment. Therefore, magnetic separation in combination with size-separation appears to be a cost-effective remediation method to remove the TBT and metals from contaminated shipyard sediments.     

Removal of Ni(II) Using Cation Exchange Resins in Packed Bed Column: Prediction of Breakthrough Curves

Sorptive removal of Ni(II) from electroplating rinse wastewaters by cation exchange resin Dueolite C 20 was investigated at the temperature of 30°C under dynamic conditions in a packed bed. The effects of sorbent bed length 0.1–0.2 m, fixed flow rate 6 dm³ min^?1, and the initial rinse water concentration (C₀) 53.1 mg L^?1 on the sorption characteristics of Dueolite C 20 were investigated at an influent pH of 6.5. More than 94.5% of Ni(II) was removed in the column experiments. The column performance was improved with increasing bed height and decreasing the flow rate. The Thomas, Yoon–Nelson, Clark, and Wolborska models were applied to the experimental data to represent the breakthrough curves and determine the characteristic design parameters of the column. The sorption performance of the Ni(II) ions through columns could be well described by the Thomas, Yoon–Nelson, and Wolborska models at effluent‐to‐influent concentration ratios (C/C₀) >0.03 and <0.99. Among the all models, the Clark model showed the least average percentage time deviation. The sorptive capacity of electroplating rinse water using Ni(II) was found to be 45.98 mg g^?1.