Application of rotating cylinder method for ecotoxicological evaluation of antifouling paints

The environmental impact of two biocide-free antifouling paints, fluoropolymer and silicone types, painted on a test cylinder was assessed using a battery of ecotoxicity test and chemical analyses for organic micro-pollutants such as perfluoroalkyl substances (PFAS). A biocide paint containing zinc pyrithione (ZnPT₂) and cuprous oxide was assessed as a positive control. A standardized laboratory rotating-cylinder method using each test cylinder with artificial seawater was performed for 45 days. After 1?h rotation, the leaked seawater was subjected for bioassay and chemical analyses twice weekly. The seawater extracts from the biocide paint showed adverse effects on bacteria, algae, and crustaceans, but those from the biocide-free paints did not. The leakage seawater from biocide-free paints, after 7-day continuous rotation, contained the same concentration levels of PFAS as blank seawater used to conduct the tests. Thus, no significant toxicities of the biocide-free paints were found under the conditions of this study. Simultaneous analysis of ZnPT₂ and copper pyrithione (CuPT₂) was developed using an HPLC with a polymeric resin column, showing that ZnPT₂ was converted to CuPT₂ by trans-chelation in the leakage seawater from the positive control paint. The experimental results using a laboratory rotating-cylinder method demonstrated that biocide-free paints did not markedly affect three species tested and no PFAS was detected. In contrast, biocide paint was significantly toxic to test species and toxicity of the extract on bacteria was partly responsible for CuPT₂ produced in leakage seawater. Thus, a laboratory rotating-cylinder method may be applied for ecotoxicological assessment of antifouling paints.     

Comparison of heavy metal concentrations in fish samples from three fish farms (Eastern Mediterranean) utilizing antifouling paints

Although aquaculture is considered the fastest growing food production industry, nevertheless there is little information regarding pollutant levels in cultured fish. Samples of cultured sea bass – Dicentrarchus labrax (Linnaeus, 1758), sea bream – Sparus aurata (Linnaeus, 1758), and sharpsnout sea bream – Diplodus puntazzo (Walbaum, 1792) from three fish farms located in the Eastern Mediterranean which utilized antifouling paints on the nets were analyzed for quantitative determination of zinc (Zn), chrome (Cr), and copper (Cu) in the gills, the liver, and the muscle separately for each tissue and fish. The results show that the highest levels of zinc (up to 29.6 mg kg^?1 dry wt) were found in the gills of all samples of sea bream and sharpsnout sea bream while in the samples of sea bass, the highest levels of zinc and chrome were found in the liver (up to 39.3 and 13.8 mg kg^?1 dry wt, respectively). Insofar, as copper is concerned the highest exposure was found in the liver of sharpsnout sea bream (up to 5.49 mg kg^?1 dry wt). The results indicate that the use of antifouling paints in aquaculture practices are a significant source of chemical pollution in cultured fish and poses a risk to the exposed organisms.     

Marine bacterial fouling: A scanning electron microscope study

A range of substrates has been examined in order to determine the types of attachment mechanism employed by marine bacteria. Use of the scanning electron microscope (SEM) has also allowed an investigation of the initimate relationship between an antifouling paint matrix and its attached bacterial community. Plastic (Thermanox) and glass coverslips, together with Cu₂O-based and TPTF-based antifouling paints and their respective empty-matrix analogues have been used in this study. Observations over periods of up to 4 wk have shown that extensive bacterial communities can develop. A variety of bacteria have been found: cocci; various rods; stalked forms; and prosthecate types. These bacteria also exhibit a range of attachment mechanisms. Initial attachment is by simple stickiness of cell walls, flagella, pili (fimbriae) or stalks. This stickiness can be attributed to an actual adhesive, electrostatic forces, electrical double-layer phenomena or to London/van der Waals forces. Often, attachment is subsequently improved by the secretion of insoluble, high molecular weight, polysaccharidic material. This material is found in the form of strands, pads, sheets or capsules and acts to bridge the space between the cell wall and substrate or adjacent cells. Thus, stalked forms are found attached by basal pads of mucilage whilst cocci and rods are often found enmeshed in mucilage strands and sheets, but less often attached by pads and capsules. Initially, single bacterial cells attach and give rise to colonies by cell division. Continuing growth of adjacent colonies leads to the development of confluent films over the substrate surface. Further growth results in thickening until eventually the entire surface is coated with a dense community of mixed bacteria together with their adhesive mucilage. In the case of antifouling paints, the porous nature of the matrix allows invasion by bacteria and the possibility of pore blockage by adhesive polysaccharides. This problem is discussed with reference to the paint's loss of antifouling efficiency.     

Comparative effects of two antifouling paints on the oyster Crassostrea gigas

The effects of two antifouling paints, one containing organotin compounds, the other copper oxide, were studied from September 1983 to October 1984 on Crassostrea gigas (Thunberg) grown under natural field conditions in the Bay of Arcachon, France. The organotin paint reduced growth rate expressed as weight, length and width, but did not affect shell height; it drastically decreased the dry condition factor and shell density, but did not affect the viability of embryos and larvae from exposed oysters. However, some decrease in larval growth rate was observed. The copper paint had no effect on oyster growth, but lowered the condition factor compared to controls. Neither viability of embryos or larvae nor larval growth were affected by this paint.     

Hinia reticulata and Nucella lapillus. Comparison of two gastropod tributyltin bioindicators

Hinia reticulata and Nucella lapillus (collected from 1989 to 1991 at Pointe de Pléneuf and Méan Mélen, France, respectively) exhibit imposex in response to tributyltin (TBT) pollution leached from antifouling paints and proved to be good TBT bioindicators. H. reticulata was kept for 18 mo under TBT-free conditions in the laboratory, but no evidence for imposex remission was found. A second series of experiments showed that food chain uptake of TBT from a contaminated diet is an important mode of TBT exposure in H. reticulata. Comparative tank experiments with H. reticulata and N. lapillus demonstrated that the same type of TBT exposure resulted in comparable TBT body burdens, biological concentration factors, and imposex development in both species [measured as increase of VDS (vas deferens sequence index), uncubed RPS (relative penis size index) and average female penis length]. Differences in imposex development of natural and laboratory populations are discussed against the background of different types of TBT contamination of their food. A statistical study, based on an analysis of natural populations of both prosobranch species, makes a comparison of the specific TBT sensitivity of the two bioindicators possible. As a consequence it is proposed that TBT biomonitoring programs in Europe should use both prosobranchs as indicator species.     

Monitoring the effectiveness of the European tributyltin regulation on the Basque coast (northern Spain) by assessing imposex in two gastropod species (Nassarius reticulatus and Nassarius nitidus)

Imposex and butyltin body burden were assessed in 2011 along the Basque coast (northern Spain) in two gastropod species (Nassarius reticulatus and Nassarius nitidus) four years after an initial survey in 2007. The aim of this re-survey was to monitor the effectiveness of the European ban on the use of tributyltin (TBT) based antifouling paints on ships’ hulls (EC 782/2003). Imposex levels in 2011 were lower than those determined in 2007 at most of the sampling sites. Accordingly, TBT concentrations in the female body burden of Nassarius reticulatus varied from 43 to 250 ng Sn/g in dry weight in 2011, which was a lower maximum than in 2007. Nevertheless, the results for the butyltin degradation index suggest that there have been recent inputs of TBT within the two main Basque harbours. Overall, the legislative measure is contributing to the reduction of TBT effects on the Basque coast although its presence is still evident.     

Wave exposure effects on population structure and recruitment in the mussel <Emphasis Type="Italic">Perna perna</Emphasis> suggest regulation primarily through availability of recruits and food,not space

Recruitment and population structure of Perna perna in low shore mussel beds were investigated over 15 months at six sites along the south coast of South Africa. Initial, subjective classification of sites as wave exposed or wave sheltered (three of each) was confirmed using the dissolution of cement blocks to measure average water flux and dynamometers for maximum wave force. Recruitment occurred throughout the year, but recruit (1–5 mm) densities were significantly higher from January to April 1996 on both shore types. Recruit densities were positively correlated with adult (>15 mm) densities for both shore types (P < 0.05) but the correlations were extremely weak (r ² < 0.06 in each case). In areas with 100% cover, adult size (mean and maximum lengths) was greater on exposed sites, but density showed the reverse and was negatively correlated with maximum wave strength (r = −0.84). Despite differences in adult densities and sizes, biomass, which is a product of the two, showed no significant difference between the two shore types (ANOVA P > 0.05). Thus wave exposure dramatically affects density, recruitment and mussel size, but not recruitment timing or biomass where there is 100% cover, and mediates a three-way interaction among food supply, larval supply and intraspecific competition for space. In contrast to shores with saturation recruitment, mussel biomass here appears to be limited by recruit supply and constraints of food, especially on sheltered shores, while density is regulated through intraspecific competition for space primarily on exposed shores and at small spatial scales.     

Environmental stress,competition and dominance of Crassostrea virginica near Beaufort,North Carolina,USA

Observations and experiments were made at 2 intertidal areas near Beaufort, North Carolina, USA from May 1977 to July 1978 to determine why the oyster Crassostrea virginica dominated the community in areas protected from wave action but not in areas directly exposed to waves. Barnacles, oysters, the green alga Enteromorpha sp. and the mussel Brachiodontes exustus were the main occupiers of primary space at the mid and low intertidal levels of exposed areas. The intertidal community at the protected site consisted of a mid intertidal occupied by the barnacles Balanus amphitrite and Chthamalus fragilis, and the oyster C. virginica, and a low intertidal dominated by C. virginica. The exposed area was highly variable with high colonization and mortality for all species producing large seasonal changes in structure. The protected site remained constant throughout the year; there was no evidence of further colonization of either barnacles or oysters and mortality was very low. Recolonization experiments, selective removal of species, and growth and survival data demonstrated that C. virginica does not become dominant at exposed locations because (1) the constant wave shock at the ocean site reduces growth and increases mortality of young and adult oysters and (2) oysters are outcompeted by the mussel B. exustus. The monopolization of space by C. virginica at protected sites contrasts with studies north of Cape Hatteras where the abundance of predators produces a more diverse and heterogeneous community. Predation was unimportant in Beaufort because predators were absent at the exposed areas and the oyster drill Urosalpinx cinerea was restricted to the subtidal zone at the protected site. This absence of predators indicates a higher level of environmental stress near Beaufort compared to areas farther north.     

Chemical Behaviour of Calcium in Stabilized Oil Ash Reef Blocks After Five Years in the Ocean

Abstract

Reef blocks made from stabilized oil ash were taken from the sea after five years in the ocean to examine the chemical behaviour of calcium. Experiments included (1) determination of the calcium leaching rate and a comparison with the rate for unexposed blocks to test the validity of a diffusion model for predicting long term (5 years) leaching rates, (2) determination of the effect of biological cover (shell) on the leaching rate, (3) determination of the leaching rate of the core of exposed reef blocks, (4) determination of the calcium content in ‘ring areas’ - regions of discoloration observed in sectioned exposed reef blocks, and (5) determination of the leachable fraction of the total calcium in exposed reef blocks. Results showed the presence of a pronounced calcium discontinuity zone located 3–7 cm from the outside surface of the reef blocks. Cumulated calcium release rates ranged from 2.81–3.14 μmol cm^?2 day^?1 for original unexposed reef blocks and the core of exposed (in the ocean for five years) blocks, respectively, to 0.47–0.50 μmol cm^?2 day^?1 for outside (facing sea water) surfaces of exposed reef blocks. Tank leaching studies also showed that the presence or absence of hard biological cover (shells) had little or no effect on the calcium release rate. the diffusion model normally used in modelling the chemical behaviour of calcium cannot be used to predict the long term (five years) leaching of calcium. the core of the exposed blocks released calcium at a rate similar to new, unexposed reef block material. Overall, it appears that the calcium discontinuity zone is probably responsible for restricting the release of calcium and hence the failure of the diffusion model.     

Studies of marine fouling and boring off Kodiak Island,Alaska

Marine fouling and boring off Kodiak Island, Alaska, was studied at depths of 5, 15, and 30 m by exposing wood/asbestos test panels and retrieving them at monthly and cumulatively longer intervals. Fouling was moderate between June and October and negligible between November and May. The fouling communities at 15 and 30 m were quite dissimilar, probably due to a large surface-to-bottom salinity gradient. The community at the 30 m level was dominated by Balanus crenatus and Pseudochitinopoma occidentalis, that at 15 m by Alcyonidium polyoum and Obelia borealis. At the 5 m deep, pierside site, the most common organisms were B. crenatus, O. borealis and Desmacystis sandalia. Borer attack was a trace at 5 and 15 m and slightly more severe at 30 m.     

Effects of nano carbon black and single-layer graphene oxide on settlement,survival and swimming behaviour of Amphibalanus amphitrite larvae

The effects of two carbon-based nanomaterials, nano-sized carbon black (nCB), and single-layer graphene oxide (GO) on settlement of Amphibalanus amphitrite (Cirripedia, Crustacea) cypris larvae (cyprids) were assessed after 24, 48, and 72 h of exposure. Additionally, the effects of these nanomaterials on the mortality and swimming behaviour of the nauplius larvae (nauplii) of the same organism were determined after 24 and 48 h. The data indicate that nCB is more effective as a potential antisettlement agent than single-layer GO; moreover, nCB did not show any adverse effects on the larvae. The swimming behaviour of II stage nauplii of A. amphitrite exposed to a suspension of nCB was inhibited only at very high nCB concentrations (≥0.5 mg/mL). Single-layer GO, on the contrary, showed lower antisettlement effects and was more active in altering the survival and inhibiting the swimming behaviour of the nauplii. An indication of the toxic or non-toxic mechanisms of the antisettlement properties of both of these nanomaterials is provided by the reversibility of the antisettlement activity. In conclusion, we propose nCB as an innovative antifouling nanomaterial that shows low toxicity towards the model organism (crustaceans) used in this study.     

Ecology of Echinometra mathaei (Echinoidea: Echinodermata) at Diani Beach,Kenya

Studies were carried out on the inner and outer coral reefs at Diani Beach on the Kenya coast to assess the distribution, density and behaviour of Echinometra mathaei (de Blainville). Transects 1 m wide were run on the two reefs in April, June and September, 1970. Test measurements on representative samples from the animal populations on both reefs were also taken. Direct observations on specimens of E. mathaci in selected rock pools on the outer reef were made to determine their movement, gregariousness, homing and feeding behaviour. Population density was higher on the inner reef furthest from the sea at low tide than on the outer reef. On the submerged inner coral reef at low tide, E. mathaei occurred mainly exposed on the seaweeds, but, on the exposed outer reef, its main niches were crevices in rock pools and under coral ledges. Sizefrequency distributions revealed that smaller individuals occurred on the inner reef and larger ones on the outer reef. The growth rate of E. mathaei was estimated from the positions of modal values, calculated from size-frequency distributions. No gregarious or homing behaviour was observed and, once settled in a suitable crevice, E. mathaei showed little movement.     

Oil-induced disruption of foraging behaviour of the asteroid keystone predator, Coscinasterias muricata (Echinodermata)

A prey-localization test allowed the observation of the foraging behaviour of Coscinasterias muricata in the presence of Mytilus edulis and the disruption of this behaviour following oil exposure. Asteroids were exposed to dilutions of water-accommodated fractions (WAF) of Bass Strait stabilised crude oil (control, 2%, 10%). Effects of exposure (4 d) and depuration (20 d) were quantified using circular statistical analyses. Observations suggested that disruption of behaviour might be concentration-dependent. Control asteroids successfully located mussels during tests. A small proportion (3 of 16) of asteroids exposed to 2% WAF also located the mussels, while asteroids exposed to 10% WAF did not. Following depuration, exposed asteroids recovered their chemoreception capacities. It is concluded that (1) Coscinasterias muricata is able to locate prey mussels through chemoreception, (2) exposure to oil disrupts its foraging behaviour, and (3) the effect is reversible. Received: 4 March 1998 / Accepted: 25 November 1998     

Effect of temperature acclimation on the metabolic rate of sea urchins

Three sea-urchin species were acclimated at 9° and 18°C for 30 days. Following acclimation, oxygen-consumption measurements were made over a broad temperature range (6° to 24°C). The effect of temperature acclimation on the metabolic rate-temperature relationship (R-T curve) was determined for each species. R-T curves of Strongylocentrotus purpuratus generally indicate no compensation (Precht type 4). Some inverse compensation (Precht type 5) is suggested at intermediate test temperatures. R-T curves of Strongylocentrotus franciscanus indicate inverse compensation particularly at intermediate test temperatures. R-T curves of Allocentrotus fragilis generally indicate no compensation. With two species, S. purpuratus and A. fragilis, greater levels of rate-temperature independence were generally reached by cold-acclimated forms at lower test temperatures and by warm-acclimated forms at higher. Rotational (slope) changes in these R-T curves may be more critical than translational (ordinate) changes.Supported in part by a National Science Foundation Institutional Sea Grant to Oregon State University.Submitted in partial fulfillment of the requirements for the degree of Master of Science, Oregon State University, June, 1970.     

Abundant ketone isolated from oily Plakortis sponge demonstrates antifouling properties

Marine sponges of the Genus Plakortis are typically unfouled; they can have a distinctive pleasant smell and an oily surface. A significant quantity of fragrant oil was obtained from a Jamaican Plakortis sp. by cryo-trap. The oil was determined to be exclusively 2-decanone. The antifouling character of the oil was evaluated by its effects on surface attachment of a gram negative bacterial model using confocal fluorescence microscopy as well as its effects on the attachment of Dreissena polymorpha (zebra mussel). The ketone dramatically inhibited attachment of the bacteria and zebra mussels. The results suggest that the oil impacts establishment of related epifauna on the Plakortis sponge in nature. Although the aliphatic ketone alone is not a potential commercial alternative for antifouling coatings, incorporating the functionality into coating design should be considered in future studies.     

Simultaneous nitrogen and silicate deficiency of a phytoplankton community in a coastal jet-front

The nutritional status of a phytoplankton community was investigated in a coastal jet-front located in the Gulf of St. Lawrence, Canada, in 1987. During the sampling period, the frontal community was mainly composed of the diatomsChaetoceros debilis, Skeletonema costatum, Thalassiosira gravida andC. pelagicus. As previously reported for the St. Lawrence, some frontal stations were depleted both in nitrate and silicate. At stations impoverished in nitrate, internal nitrate pool concentrations were low or undetectable, suggesting that cells had not, recently, been exposed to a nitrate flux which exceeded the nitrate assimilation rate. At these impoverished stations, however, ambient and intracellular concentrations of ammonium and urea were high, suggesting that the community was not nitrogen-deficient. The comparison between the ambient silicate concentrations and the silicate requirement (K _s ) of the dominant diatoms suggests thatC. debilis andS. costatum were Si-deficient. This is further supported by the low silicate uptake rates and intracellular concentrations measured at the silicate impoverished stations. The silicate deficiency also resulted in a decrease in the seston and phytoplankton N:C ratios.Please address all correspondence and requests for reprints to Dr Levasseur at his new address: Maurice Lamontagne Institute, 850 Route de la Mer, Mont-Joli, Québec G5H 3Z4, Canada     

Functional morphology of Petricola (Rupellaria) typica (Bivalvia: Petricolidae)

The bivalve Petricola typica occurs from North Carolina (USA) to Brazil where, according to Rios (1970), its range extends to Rio Grande do Sul. The species can be found in coral blocks of Mussismilia hispida, inside colonies of Schizoporella unicornis (a calcarean bryozoan) and, more frequently, inside the sandy reefs built by the polychaete Phragmatopoma lapidosa (intertidal zone). Initial settlement probably occurs in a pre-existing cavity, which is enlarged to form a hole into which the bivalve fits exactly when its valves open. The shell, mantle, and siphons are described in detail. Special attention was paid to the ctenidia, labial palps, and stomach.     

Application of microcosm and species sensitivity distribution approaches in the ecological hazard assessment of 4-tert-butylphenol

In order to evaluate the ecological hazard of 4-tert-butylphenol (4-TBP), species abundances and physicochemical properties were monitored for 63 days in a microcosm system containing planktonic algae, rotifers, shrimps and Daphnia. The 63 days-NOEC (no observed effect concentration) of 4-TBP for this system was calculated. At the same time, species sensitivity distribution curves were constructed based on the toxicity data of EC₁₀, EC₅₀ and NOEC derived from laboratory single-species toxicity tests, which further gives no obvious hazard concentrations for 95% species in the ecosystem (HC₅). In both the microcosm and the single-species tests, the shrimp (Neocaridina sp.) was the most sensitive species to 4-TBP exposure, while most algae species were relatively insensitive compared to the zooplankton. For the microcosm exposed to 4-TBP, significant changes occurred to the community structure instead of the community function, resulting in a NOEC_microcosm of 265.38?μg?L^–1 which approached the EC₁₀-based HC₅ (0.376?mg?L^–1). Nevertheless, EC₅₀-based HC₅ was higher than the NOEC_microcosm, and the NOEC-based HC₅ was lower. The data showed that the EC₁₀-based HC₅ was protective at the similar level with the result of microcosm for 4-TBP, providing supportive data for chemical risk assessment.