Imposex in Morula Granulata as Bioindicator of Tributyltin (TBT) Contamination in the Dampier Archipelago, Western Australia

This study was undertaken to examine the use of imposex in the tropical neogastropod whelk Morula granulata as bioindicator of tributyltin (TBT) contamination. Samples were collected from sites throughout the Dampier Archipelago; both impact sites close to intensive shipping activity and remote control sites. TBT in this area originates mainly from commercial vessels using the Port of Dampier that are >25 m in length and exempt from legislation controlling the use of TBT in antifouling paints. A field survey was undertaken in July 1997; 100 M. granulata were taken at each of 18 sites with varying vessel activity, and examined for imposex. The level of TBT contamination in the Archipelago was low; ranging from <0.3 to 25 ng Sn l⁻¹ in water,<0.3 to 80 ng Sn g−¹ in oyster tissue (Saccostrea cuccullata – prey of M. granulata), and <0.3 to 33 ng Sn g⁻¹ in whelks. Percentage of imposex in M. granulata ranged from 0% to 57%, and was correlated with distance to vessel activity (r=0.646, p<0.05). The only significant relationship of imposex with butyltin concentrations was with TBT in oysters (r=0.826, p<0.05), and dibutyltin (DBT) in whelks (r=0.783, p<0.05). It is postulated that this is because of interspecies variation in ability to metabolize TBT to DBT and MBT (monobutyltin), as well as induction of imposex in earlier life stages, so that imposex in adults could be a reflection of prior contamination. M. granulata is a suitable bioindicator of TBT contamination in the Dampier Archipelago, which could be used throughout the Indo-Pacific given its abundance in the region.     

Differences in the acute toxicities of tributyltin between the Caprellidea and the Gammaridea (Crustacea: Amphipoda)

Tests for the acute toxicity of tributyltin (TBT) were conducted on amphipod crustaceans collected from Otsuchi Bay, Japan. Five species of caprellids and three species of gammarids, which belong to a closely related ecological niche, were used for the exposure experiments at seven test concentrations (0, 0.001, 0.01, 0.1, 1, 10 and 100 microg TBTCl/l) for 48 h at 20 degrees C. The 48-h LC50 values of the caprellids were 1.2-6.6 microg TBTCl/l, and these were significantly lower than those of the gammarids (17.8-23.1 microg TBTCl/l). This suggests that caprellids are more sensitive to TBT than gammarids. Furthermore, the proportions of TBT and its derivatives, dibutyltin (DBT) and monobutyltin (MBT), were measured in the amphipods collected from Otsuchi Bay. In the caprellids, TBT was the predominant compound, accounting for 72% of the total butyltin which reflected the butyltin ratio in seawater, while in the gammarids, TBT's breakdown products (DBT and MBT) predominated, accounting for 75% of the total butyltin. This difference suggests that caprellids may have lower metabolic capacity to degrade TBT than gammarids. Therefore, the difference in sensitivity to TBT among the amphipods is thought to be related to the species-specific capacity to metabolize TBT.     

Concentrations of organotin compounds in blue mussels from the wharves of Tokyo Bay

Organotin compounds (tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPT), diphenyltin (DPT), and monophenyltin (MPT)) were quantified in blue mussels, Mytilus edulis, in 1989 at 26 wharves along Tokyo Bay. Organotin compounds, other than DPT, were detected in all mussel samples (in case of DPT: 23 of 26). The concentration of DBT was highest among butyltin compounds and that of TPT was highest among phenyltin compounds. The results showed that relatively high concentrations of organotin compounds persist in blue mussels of Tokyo Bay, although the use of the paints containing these compounds has been limited for several years by regulations.     

Taxonomic composition and seasonality of diatoms in three Dinaric karstic lakes in Croatia

The composition and temporal distribution of planktonic diatoms were studied in three small shallow karstic lakes – Modro Oko, Desne, and Kuti – throughout the seasons in 1994, 1995, 1997, and 1998. Physico-chemical parameters did not differ among the three lakes, except for NO₃ concentrations. Altogether, 137 diatom taxa within 41 genera were found in all three lakes combined. The highest number of taxa belonged to the genera Surirella (13), Navicula (12), andCymbella (9). Most taxa were tychoplanktonic, with true panktonic taxa contributing only 14% of the total. Despite their physical-chemical similarity, the lakes showed differences in the structure and dynamics of their diatom communities. Blooms occurred at different times in each of the lakes, and community similarity (Jaccard index) among all three was low (17.6–29.1%). The highest mean values of surface diatom abundance in Modro Oko (2199 cells L⁻¹), Desne (7900 cells L⁻¹), and Kuti (20690 cells L⁻¹) were not significantly different. Margalef's species richness index did not differ either among the lakes or seasonally. Only five diatom taxa in quantitative samples, and 22 taxa in net-samples, were common to all lakes. The most frequent diatoms were Cyclotella striata (56–93%), Fragilaria ulna (50–67%), and Asterionella formosa (27–83%). The most abundant taxa in Modro Oko, Desne, and Kuti were, respectively, Cymbella sp. 1 (402 cells L⁻¹), Cyclotella striata (3000 cells L⁻¹) and Asterionella formosa (20690 cells L⁻¹). Eighteen taxa were recorded for the first time in Croatia: Amphora commutata, Caloneis amphisbaena var. subsalina, C. silicula var. peisonis, Campylodiscus echeneis, Coscinodiscus lacustris, Denticula elegans, Gyrosigma acuminatum var. lacustre, G. distortum var. parkeri, G. fasciola, Navicula menisculus var. menisculus, N. pusilla, N. helensis, Stauroneis parvula var. prominula, Staurosira construens f. subsalina, Stephanodiscus sp. 1, Surirella gracilis, S. ovalis, and S. striatula. The genus Stephanodiscus was recorded for the first time in Croatia.     

Calibrations for benthic foraminiferal Mg/Ca paleothermometry and the carbonate ion hypothesis

Benthic foraminiferal magnesium/calcium ratios were determined on one hundred and forty core-top samples from the Atlantic Ocean, the Norwegian Sea, the Indian Ocean, the Arabian Sea and the Pacific Ocean, mostly at sites with bottom water temperatures below 5 °C. Mg/Ca ratios are consistently lower, by  0.2 mmol/mol, in samples cleaned using oxidative and reductive steps than using oxidative cleaning. Differences between Cibicidoides species have been identified: Mg/Ca of Cibicidoides robertsonianus > Cibicidoides kullenbergi > Cibicidoides wuellerstorfi. Comparison with bottom water temperatures support observations of lowered Mg/Ca of C. wuellerstorfi at temperature below  3 °C compared with values predicted by published calibrations and from other Cibicidoides species. Hydrographic data shows that carbonate ion saturation (Δ[CO₃²⁻]) decreases rapidly below this temperature. An empirical sensitivity of Δ[CO₃²⁻] on Mg/Ca has been established for C. wuellerstorfi of 0.0086 ± 0.0006 mmol/mol/μmol/kg. A novel application using modern temperatures and Last Glacial Maximum temperatures derived via pore fluid modelling supports a carbonate ion saturation state effect on Mg incorporation. This may significantly affect calculated δ¹⁸O_seawater obtained from foraminiferal δ¹⁸O and Mg/Ca temperature.     

Continuing observation of disturbed reproductive cycle and ovarian spermatogenesis in the giant abalone, Haliotis madaka from an organotin-contaminated site of Japan

Histological examination of gonads as well as chemical analysis of organotin compounds in tissues of the giant abalone, Haliotis madaka, was conducted to evaluate continuing endocrine disruption in abalone populations in Japan. Abalone specimens were collected from two different areas, Tsushima as a reference site and Jogashima as a site representative of declining abalone populations where serious organotin contamination had been observed, each month from January 1998 to March 1999. Scores were given to the development stages of reproductive cells in the ovary and testis. The degree of sexual maturation was evaluated by calculating the mean value of a histogram of these scores for the reproductive cells of each abalone. The temporal variations in degree of sexual maturation showed that female and male abalone from Tsushima matured synchronously, while those from Jogashima did not, which were similar to results of the previous study during September 1995–November 1996. Approximately 19% of the female abalone from Jogashima were masculinized with an ovo-testis, which was also similar to the result of the previous study. The masculinization of female abalone is reported to be induced by tributyltin (TBT) and triphenyltin (TPhT) from antifouling paints. Concentrations of the sum of butyltins (TBT, dibutyltin (DBT) and monobutyltin (MBT): ΣBTs) and the sum of phenyltins (TPhT, diphenyltin (DPhT) and monophenyltin (MPhT): ΣPhTs) in the muscle of abalone from Jogashima (n = 73) of 7.8 ± 9.0 ng/g wet wt. and 4.5 ± 6.8 ng/g wet wt., respectively, were significantly higher than those from Tsushima (n = 87) of 4.7 ± 4.9 ng/g wet wt. and 0.8 ± 1.7 ng/g wet wt., respectively (p < 0.05 for ΣBTs; p < 0.001 for ΣPhTs), although concentrations of TBT and TPhT in the muscle of abalone from Jogashima (n = 73) of 2.2 ± 2.5 ng/g wet wt. and 5.8 ± 5.1 ng/g wet wt., respectively, were insignificantly and significantly higher than those from Tsushima (n = 87) of 0.4 ± 0.6 ng/g wet wt. and 0.5 ± 0.9 ng/g wet wt., respectively, (p > 0.05 for TBT; p < 0.001 for TPhT). Thus, endocrine disruption as well as contamination by organotins in the giant abalone from Jogashima is still persisting.     

Removal of tributyltin (TBT) by live and dead microalgal cells

The removal of tributyltin (TBT) from artificial wastewater by dead and live cells of four microalgal species, Chlorella miniata, C. sorokiniana, Scenedesmus dimorphus and S. platydiscus was investigated. Dead cells were generally more efficient in removing TBT during three days exposure. More than 90% and 85% TBT were removed by dead cells of Scenedesmus and Chlorella, respectively. Although the removal percentages of live microalgae were smaller, TBT was continuously absorbed and degraded, and TBT removal percentages similar to respective dead cells were achieved at the end of 14 days treatment. Degradation products, DBT and MBT, were recorded mainly inside the cells, and intracellular MBT concentrations were significantly higher than DBT. In terms of TBT removal, Scenedesmus cells were more effective than Chlorella, probably due to larger cell sizes and biomass. However, TBT specific uptake and degradation by Chlorella was higher than in Scenedesmus. The highest specific TBT uptake values, as well as the highest degradation, were recorded in C. miniata, a Hong Kong isolate.     

A study on the treatment of antifouling paint waste from shipyard

A study on the treatment of antifouling paint waste from shipyards, including sandblast waste and ship hull washing wastewater, was performed. The sandblast waste could be effectively detoxified by heat treatment, and the efficiency was affected by the temperature of the heating vessel and treatment time. The removal efficiency of total organotin compounds from the sandblast waste was over 99% at 1000 °C and treatment for 1 h. For the treatment of ship hull washing wastewater by the solvent extraction, ship diesel was a good solvent for the tributyltin (TBT) extraction, and the proper amount of solvent was about 10 mL for TBT extraction from 1 L of wastewater. The extraction efficiency of TBT was significantly affected by the agitation intensity. The TBT in the wash wastewater was rapidly extracted within 1 h. The level of the TBT residual in the wastewater extracted for 1 h was 2.8 μg L⁻¹, and this was further decreased to 0.8 after 5 h extraction.     

Contamination by persistent organochlorines and butyltin compounds in the west coast of Sri Lanka

Concentrations of polychlorinated biphenyls (PCBs), dichlorodiphenyl trichloroethane and its metabolites (DDTs), isomers of hexachlorocyclohexane (HCHs), hexachlorobenzene (HCB), chlordane compounds (CHLs) and butyltin compounds (mono-, di- and tributyltin) were determined in biota and sediments collected from locations on the west coast of Sri Lanka. The PCB concentrations found in fish from the Kelani River mouth were higher than those from other Asian developing countries. The pattern of organochlorine accumulation was in the order of PCBs > DDTs > CHLs > HCHs > HCB, and resembled those reported for most developed countries. The accumulation pattern of butyltins in fish was in the order of TBT > DBT > MBT suggesting recent exposure to TBT sources. Total butyltin concentrations found in rabbit fish liver (11-38 micrograms/g wet wt), collected from the Colombo dockyard, could be the highest ever reported for fish in the world.     

Effects of tributyltin at concentrations below ambient levels in seawater on Caprella danilevskii (Crustacea: Amphipoda: Caprellidae)

Hatched juveniles of Caprella danilevskii (Crustacea: Amphipoda) were exposed to one of two concentrations of tributyltin (TBT) (1.1 and 10.7 ng TBTL(-1)) for 49 d at 20 degrees C. These concentrations are near or below ambient levels in seawater. In both treatments and control, the survival rate was 100% at maturation, and >85% at the end of the experiments. Females reached maturation at 20 (median) to 21.5d at instar VII, and repeated spawning 4-5 times during the experiment. The total number of juveniles per female decreased significantly from 39.5 in the control to 24.5 and 17.5 in 1.1 ng L(-1) and 10.7 ng L(-1) treatments, respectively. An earlier study reported that as the TBT concentration in seawater increased from a 0-10 ng L(-1) regime to a 10-20 ng L(-1) regime, the number of stations where Caprella spp. could be collected decreased along the coast of the Seto Inland Sea, of Japan. Thus, the present study indicates the possibility that the extremely low concentration of TBT measured in Japanese waters after 2000 lead to a reduction in reproductive success of Caprella spp.     

Assessment of organotin (butyltin species) contamination in marine biota from the Eastern Aegean Sea, Turkey

The marine environment continues to be adversely affected by tributyltin (TBT) release from maritime traffic. Therefore the concentrations of TBT, dibutyltin (DBT) and monobutyltin (MBT) were measured in barnacles, mussels and fish along the Eastern Aegean coastline. The average concentrations of TBT ng Sn g⁻¹ were found to be 235 in fish, 116 in mussels and 635 in barnacles. The highest concentrations of TBT, DBT and MBT were observed in the barnacles which had been sampled in marinas and harbors. All mussels sampled showed values of TBT + DBT, which were below the “tolerable average residue level (TARL)” as currently accepted. This indicates a lack of risk to the consumer. However, 7 out of the 15 fish sampled displayed TBT + DBT levels above the TARL, which indicates that a fish consumer group may be at risk. Barnacles have high potential as biomonitors for the presence of organotin in the Aegean Sea.     

Simulations of accidental coal immersion

Coal is currently becoming an increasingly interesting fossil energy resource and that is the reason why its maritime transport, and hence the risk of collier accidents, increase. In this work, the environmental impact of an accidental coal immersion at sea is studied: the physicochemical effects are estimated using innovative experimental setups – a laboratory seawater canal called “polludrome” is used to evaluate the behaviour of coal particles submitted to a seawater flow, and a specifically designed tub is used to study the physicochemical consequences induced when coal is introduced into continuously renewed seawater. When coal is introduced into seawater, the most easily visible consequences are physical: fine coal particles reduce the daylight penetration up to 100% and move along with the flow, and coal chunks accumulate on the floor. Chemical effects are also measured: humic matters are dissolved from coal into seawater (up to 2 mg L⁻¹), but no release of polycyclic aromatic hydrocarbons is evidenced. Some inorganic compounds are dissolved, among which manganese, whose concentrations can reach 1 μg L⁻¹. Fortunately, the results show that the environmental impact of this type of accident would remain limited.     

Distribution of butyltins in the waters and sediments along the coast of India

Water and surface sediment samples were analyzed for butyltins (TBT, DBT, MBT) from various ports along the east and west coast of India. The total butyltin (TB) in water samples varied between ∼1.7 and 342 ng Sn l⁻¹, whereas for sediments it varied between below detection limit to 14861 ng Sn g⁻¹ dry weight of sediment. On an average Chennai port recorded the highest level of butyltins in the sediments while Paradip recorded the highest level of butylins in the waters. A fairly good relationship between the TB in the sediment and overlying water samples, as well as between organic carbon and TB, implicates the importance of adsorption/desorption process in controlling the levels of TBT in these port areas. In India the data on organotin pollution is very sparse; most of the port areas have been surveyed for butyltins for the first time during this study.     

Calcium alginate immobilized marine microalgae: experiments on growth and short-term heavy metal accumulation

Growth of 11 calcium alginate immobilized marine microalgal species belonging to eight taxonomical groups has been checked in the present work. Cellular densities inside the calcium alginate beads were monitored during 17 days. Good growth and maintenance of the structure of the beads were both found for some of the assayed species. One of those species (Tetraselmis chui, Prasinophyceae) was selected in order to perform a short term (up to 24 h) heavy metal accumulation experiment. Beads of calcium alginate containing (or not) cells of T. chui were exposed to 820 μg L⁻¹ Cu and 870 μg L⁻¹ Cd separately during a 24 h period, and accumulation of heavy metals in the beads was measured after this time and compared. Concentration of each metal in the supernatants was monitored at 5, 10, 60 min and 24 h from the beginning of the experiment. After 24 h, practically all Cu was removed by the beads. Beads with immobilized algae removed around 20% of total Cd, while beads without algae removed half of that percentage.     

Development of a 2-km resolution ocean model covering the coastal seas around Japan for operational application

Ocean Dynamics - In order to expand the coastal ocean monitoring and forecasting system of the Japan Meteorological Agency from the Seto Inland Sea to the entire coastal seas of Japan, a 2-km...     

Hydrogen peroxide production rates in clean and polluted coastal marine waters of the Mediterranean, Red and Baltic Seas

The main aim of this study was to assess the hydrogen peroxide (HP) production rates (HPPR) related to anthropogenic pollution in coastal waters by laboratory and field experiments. HPPR's were assessed by simultaneous measurements of HP concentrations, cumulative solar UV irradiation and dissolved organic matter (DOM) fluorescence in the seawater samples at clean and polluted sites in the Mediterranean, Red and the Baltic Seas. The natural HP concentrations at all sites (8–100 nM) fall within the normal range recorded elsewhere, and follows a diurnal pattern. The polluted stations in the Mediterranean and Baltic Seas showed higher HPPR (3.2–16.6 nM m² W⁻¹ h⁻¹) than the clean stations, while in the Red Sea no significant differences were found because the station that was considered a priori polluted was actually rather clean (2–3 nM m² W⁻¹ h⁻¹). Laboratory experiments demonstrated that HPPR was positively linearly correlated to DOM fluorescence, however, this relationship was not found in the natural seawater samples examined in the field. The lack of relationship between HPPR and DOM in the field was attributed to enzymatic breakdown of HP as observed in dark decay experiments. HP dark decay rates were highest in polluted stations, probably due to larger bacterioplankton populations in these samples. Moreover, the HP dark decay rates were much lower in filtered than in non-filtered samples. Sun incubation of filtered (0.2 μm) seawater samples were performed to assess whether elimination of particles would yield higher HPPRs than in non-filtered samples. In the Baltic Sea (low UV irradiation) HPPR was higher in the filtered samples, while at sites with relatively high UV irradiation (Mediterranean and Red Seas), filtration of seawater did not stimulate HPPRs, probably due to UV-damage to planktonic microorganisms.     

Baseline of butyltin pollution in coastal sediments within the Basque Country (northern Spain), in 2007-2008

Tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) were measured in surficial sediments at, the ports of Pasaia and Bilbao, together with other mid- and small-size harbours of the Basque Country (northern Spain), in 2007-2008. The highest values of the sum of the three measured butyltin species (3523-3640 ng g⁻¹, as Sn) were found at sampling stations near to shipyards located within the port of Pasaia. The highest value of TBT concentration (3143 ng g⁻¹, as Sn) was found at the marina of Getxo, in the port of Bilbao. The degree of TBT degradation varied greatly between sampling stations, being found to be generally higher in those sediments with higher values of redox potential and lower values of TBT concentration (normalized by organic matter content).     

Nutrient dynamics in Mediterranean temporary streams: A case study in Pardiela catchment (Degebe River, Portugal)

Most of the streams in the Mediterranean region are temporary, following predictable seasonal of flooding and drying, with a transition from lotic conditions to shallow lentic conditions. The goal of our study was to assess the nitrogen and phosphorus dynamics in channel-bed processes of temporary streams between floods. Results show that, during winter, temperatures ranged between 9.5 and 11.2 °C and oxygen concentration ranged from 8.0 to 9.5 mg L⁻¹, whereas, during summer, temperatures varied between 21.2 and 26.8 °C and oxygen between 1.2 and 5.3 mg L⁻¹, with oxygen depletion in the pools during the night. The nitrate concentrations were far more abundant during winter (February), while ammonium concentration increased after stream fragmentation into pools (especially in July when oxygen depletion conditions favoured ammonification). Results on sediment profiles showed that the most active sediment layers for NH₄-N are the top 2–3 cm, corresponding to the sediment depositional sites of the stream. Phosphate concentrations had larger variability, yet concentrations decreased from winter to spring and increased again in summer, when the shallow water pools were formed. Sediment profiles at the sediment depositional sites showed that PO₄-P was more dynamic in the first 6 cm.

In Mediterranean temporary streams, nutrient dynamics vary seasonally, as the system transits from lotic conditions to shallow lentic conditions, evidencing the regeneration of nutrients from organic and inorganic matter during the flow cessation period.     

REE diffusion in calcite

Chemical diffusion of four rare-earth elements (La, Nd, Dy and Yb) has been measured in natural calcite under anhydrous conditions, using rare-earth carbonate powders as the source of diffusants. Experiments were run in sealed silica capsules along with finely ground calcite to ensure stability of the single-crystal samples during diffusion anneals. Rutherford backscattering spectroscopy (RBS) was used to measure diffusion profiles. The following Arrhenius relations were obtained over the temperature range 600–850°C: D_La =2.6×10⁻¹⁴ exp(−147±14 kJ mol⁻¹/RT) m² s⁻¹, D_Nd =2.4×10⁻¹⁴ exp(−150±13 kJ mol⁻¹/RT) m² s⁻¹, D_Dy =2.9×10⁻¹⁴ exp(−145±25 kJ mol⁻¹/RT) m² s⁻¹, D_Yb =3.9×10⁻¹² exp(−186±23 kJ mol⁻¹/RT) m² s⁻¹. In contrast to previous findings for refractory silicates (e.g. zircon), differences in transport rates among the REE are not pronounced over the range of temperature conditions investigated in this study. Diffusion of the REE is significantly slower than diffusion of the divalent cations Sr and Pb and slower than transport of Ca and C at temperatures above 650°C. Fine-scale zoning and isotopic and REE chemical signatures may be retained in calcites under many conditions if diffusion is the dominant process affecting alteration.     

Effects of some environmental parameters on the reproduction and development of a tropical marine harpacticoid copepod Nitocra affinis f. californica Lang

The effects of salinity, temperature, and light conditions on the reproduction and development of harpacticoid copepod, Nitocra affinis f. californica under controlled laboratory conditions were determined. Seven different salinity levels (5, 10, 15, 20, 25, 30, 35 ppt), four temperatures (20, 25, 30, 35 °C), three different light intensities (25, 56, 130 μmol m⁻² s⁻¹) and photoperiods (24 h:0 h, 1 h:23 h, 12 h:12 h LD cycle) were employed in this study. The highest (p < 0.05) overall reproduction and fastest development time were achieved by copepods reared under 30–35 ppt salinity. The optimum temperature required for the maximum reproduction was 30 °C while under 30 °C and 35 °C the copepod development time was shortest (p < 0.05) compared to other temperature levels. The overall reproduction was highest (p < 0.05) and development rate of N. affinis was shortest (p < 0.05) under lowest light intensity (25 μmol m⁻² s⁻¹). Continuous light (24 h:0 h LD) inhibited the egg production while, continuous darkness (1 h:23 h LD) and 12 h:12 h LD significantly favoured the overall reproductive activity of the female. Photoperiods 1 h:23 h and 12 h:12 h LD yielded highest total (p < 0.05) offspring female⁻¹ coupled with highest (p < 0.05) survival percentage. This study illustrated that although N. affinis can tolerate wide range of environmental conditions, prolonged exposure to subnormal environments affect its reproduction and development. This study showed that this species can be mass cultured for commercial purposes and has a potential to be used for toxicity studies due to its high reproductive performance fast development and a wide range of tolerance to environmental conditions.