Marine pollution from antifouling paint particles

Antifouling paint particles (APP) are generated during the maintenance of boats and are shed from abandoned structures and grounded ships. Although they afford a highly visible, colourful reflection of contamination in the vicinity of the source, little systematic study has been undertaken regarding the distribution, composition and effects of APP in the wider marine environment. This paper reviews the state of knowledge in respect of APP, with particular emphasis on those generated by recreational boatyards. The likely biogeochemical pathways of the biocidal and non-biocidal metals in current use (mainly Cu and Zn) are addressed in light of recent research and an understanding of the more general behaviour of contaminants in marine systems.Analyses of paint fragment composites from recreational facilities in the UK reveal chemical compositions that are similar to those representing the net signal of the original formulations; significantly, dry weight concentrations of Cu and Zn of up to about 35% and 15%, respectively, are observed and, relative to ambient dusts and sediment, elevated concentrations of other trace metals, like Ba, Cd, Cr, Ni, Pb and Sn, occur. These metals leach more rapidly from APP than a painted surface due to the greater surface area of pigments and additives exposed to the aqueous medium. In suspension, APP are subject to greater and more rapid environmental variation (e.g. salinity, pH, dissolved oxygen) than painted hulls, while settled APP represent an important source of persistent and degradable biocides to poorly circulating environments. Through diffusion and abrasion, high concentrations of contaminants are predicted in interstitial waters that may be accumulated directly by benthic invertebrates. Animals that feed non-selectively and that are exposed to or ingest paint-contaminated sediment are able to accelerate the leaching, deposition and burial of biocides and other substances, and represent an alternative vehicle for contaminant entry into the marine foodchain. Clearly, an extensive understanding of biocide behaviour on painted surfaces is not sufficient for predictive or management purposes regarding APP. Greater caution is required by boaters and boatyards during the removal and disposal of solid wastes, and more awareness or stricter enforcement of relevant codes of practice or legislation is recommended.     

Trace metals in antifouling paint particles and their heterogeneous contamination of coastal sediments

Antifouling paint residues collected from the hard-standings of a marine leisure boat facility have been chemically characterised. Scanning electron microscopy revealed distinct layers, many containing oxidic particles of Cu and Zn. Quantitative analysis indicated concentrations of Cu and Zn averaging about 300 and 100 mg g⁻¹, respectively, and small proportions of these metals (<2%) in organometallic form as pyrithione compounds. Other trace metals present included Ag, Cd, Cr, Ni, Pb and Sn, with maximum concentrations of about 330, 75, 1200, 780, 1800 and 25,000 μg g⁻¹, respectively. Estuarine sediment collected near a boatyard contained concentrations of Cu and Zn an order of magnitude greater than respective concentrations in “background” sediment, and mass balance calculations suggested that the former sample was contaminated by about 1% by weight of paint particles. Clearly, antifouling residues represent a highly significant, heterogeneous source of metallic contamination in the marine environment where boating activities occur.     

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.     

A new bioassay for the inspection and identification of TBT-containing antifouling paint

Since the 1960s tributyl (TBT)-based antifouling paints are widely applied to protect ship’s hulls from biofouling. Due to its high toxicity to aquatic ecosystem most of the countries (28 nations in 2008) signed the AFS convention to control the use of harmful antifouling systems on ships. Nevertheless there is currently no simple method to control the presence of organotin in paint. In this study, we propose a bioassay based on the use of a recombinant bioluminescent bacteria to detect directly in paint the presence of TBT. We also propose a simple device as an inspection system to control the absence of organotin in the ship’s hull paint. The presence of organotin could be revealed in less than three hours.     

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.     

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.     

Inhibition of coral photosynthesis by the antifouling herbicide Irgarol 1051

International regulation of organotin compounds for use in antifouling paints has led to the development and increased use of replacement compounds, notably the s-triazine herbicide Irgarol 1051. Little is known about the distribution of Irgarol 1051 in tropical waters. Nor has the potential impact of this triazine upon photosynthesis of endosymbiotic microalgae (zooxanthellae) in corals been assessed. In this study Irgarol 1051 was detected in marinas, harbours and coastal waters of the Florida Keys, Bermuda and St. Croix, with concentrations ranging between 3 and 294 ng 1(-1). 14C incubation experiments with isolated zooxanthellae from the common inshore coral Madracis mirabilis showed no incorporation of H14CO3- from the sea water medium after 4-8 h exposure to Irgarol 1051 concentrations as low as 63 ng 1(-1). Reduction in net photosynthesis of intact corals was found at concentrations of l00 ng 1(-1) with little or no photosynthesis at concentrations exceeding 1000 ng 1(-1) after 2-8 h exposure at all irradiances. The data suggest Irgarol 1051 to be both prevalent in tropical marine ecosystems and a potent inhibitor of coral photosynthesis at environmentally relevant concentrations.     

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.     

Effects of new antifouling compounds on the development of sea urchin

Tributyltin oxide (TBTO) has been used worldwide in marine antifouling paints as a biocide for some time. However, it produced toxic effects, especially in marine water/sediment ecosystems. Consequently, its use in antifouling paints has been prohibited in many countries. In this study, the toxicity of alternative and/or new antifouling biocides compared with TBTO is assessed by a biological method. The effects of these chemicals on marine species have not been well studied. This paper assesses, comparatively, the effects of eight biocides on sea urchin eggs and embryos. The chemicals assessed were TBTO, Irgarol 1051, M1 (the persistent degradation product of Irgarol), Diuron, zinc pyrithione, 'KH101', 'Sea-Nine 211', and copper pyrithione. For these chemicals, toxicity appears to be in the order zinc pyrithione > Sea-Nine 211 > KH101 > copper pyrithione > TBTO > Diuron approximately = Irgarol 1051 > M1. Here, we show that zinc pyrithione, Sea-Nine 211, KH101, and copper pyrithione are much more toxic to sea urchins than TBTO or the other chemicals.     

A survey of antifoulants in sediments from Ports and Marinas along the French Mediterranean coast

Due to deleterious effects on non-target organisms, the use of organotin compounds on boat hulls of small vessels (<25 m) has been widely prohibited. The International Maritime Organisation (IMO) resolved that the complete prohibition on organotin compounds acting as biocides in antifouling systems should commence in 2008. As a result of restrictions on the use of organotin based paints, other antifouling formulations containing organic biocides have been utilised. This survey was conducted to assess the contamination of replacement biocides in the marine environment following the ban of TBT-based paints. Surface sediments samples were collected in the major ports and marinas along the France Mediterranean coastline (Cote d’Azur) and analysed for organotin compounds, Irgarol 1051, Sea-nine 211^TM, Chlorothalonil, Dichlofluanid and Folpet. Every port and marina exhibited high levels of organotin compounds, with concentrations in sediments ranging from 37 ng Sn g⁻¹dry wt in Menton Garavan to over 4000 ng Sn g⁻¹dry wt close to the ship chandler within the port of Villefranche-sur-Mer. TBT degradation indexes suggested that fresh inputs are still made. Among the other antifoulants monitored, only Irgarol 1051 exhibited measurable concentrations in almost every port, with concentrations ranging from 40 ng g⁻¹dry wt (Cannes) to almost 700 ng g⁻¹dry wt (Villefranche-sur-Mer, ship chandler).     

A mechanistic study on the photodegradation of Irgarol-1051 in natural seawater

The kinetics of the photoinduced degradation and transformation of the antifouling booster biocide, Irgarol-1051, in natural coastal seawater was studied. The measured first-order rate constant for the degradation of Irgarol-1051 was 4.02 ± 0.1 × 10⁻⁴ h⁻¹, while the rate constant for the formation of 2-methylthio-4-tert-butylamino-6-amino-s-triazine (M1), the most dominant degradation product of Irgarol-1051, was 4.6 ± 0.1 × 10⁻⁵ h⁻¹. This considerably slower rate suggested that the transformation of Irgarol-1051 to M1 may not be the predominant pathway of the photodegradation process. During the photodegradation study, a new s-triazine species was observed in the degradation mixtures which, together with M1, appeared immediately upon photolysis and continued to accumulate in the degradation mixture throughout the entire study duration. This is in contrast to the behaviour of the recently identified degradation product of Irgarol-1051, 3-[4-tert-butylamino-6-methylthiol-s-triazin-2-ylamino]- propionaldehyde (M2), which was only detected in the degradation mixture after a long induction period. High-resolution tandem mass spectrometric analysis hinted that the new degradation product (M4) may possess a terminal alcohol and is likely to be an N-allylic alcohol derivative of M1. This suggests that M4 may, indeed, be a precursor of M2 via redox transformation at its N-allylic alcohol functionality.     

Effects of antifouling paint components (TBTO,copper and triazine) on the early development of embryos in cod (Gadus morhua L.)

To assess the risk of antifoulant use to the commercially important cod (Gadus morhua L.), fertilised cod eggs were exposed to triazine, copper and TBTO singly or combined in laboratory tests with running seawater. At the highest tested concentrations (11.5 microg Cu l(-1); 5 microg TBTO l(-1)) larval mortality was increased. The highest concentration of triazine (40 microg l(-1)) did not cause any significant mortality. Fertilised eggs that had been exposed to all the three chemicals singly for five days showed a higher buoyancy than the controls. No synergistic or antagonistic effects were indicated. Embryos/larvae exposed to 0.004-0.8 microg TBTO l(-1) did not show any changed respiration compared to the controls after hatching. It is concluded that existing known field concentrations of the three antifoulants are hardly expected to cause detectable effects on fish embryonic/larval development.     

Effects of local site conditions on the seismic response of municipal solid waste landfills

Over the last decade, the seismic response of landfills made of municipal solid waste has drawn attention mainly due to the environmental and public-health issues that could be raised in the event of a failure. Nevertheless, there are several associated technical issues that have not been adequately investigated. One of these is the impact of local site conditions on the earthquake-induced accelerations and, thereby, on the seismic design of a landfill. This study presents the results of a parametric numerical simulation that has been performed in order to examine the effects of local site conditions on the dynamic response of a typical landfill. Emphasis is given on the special characteristics of ground motion, while the material nonlinearity of both soil and waste is taken into account by an equivalent-linear procedure. Results indicate that local site conditions may play a significant role in the seismic response of a landfill. However, this role cannot be judged a priori as beneficial or detrimental, as it depends not only on soil conditions and seismic excitation, but also on the material and geometric characteristics of the landfill.     

Recovery from imposex by a population of the dogwhelk, Nucella lapillus (Gastropoda: Caenogastropoda), on the southeastern coast of England since May 2004: A 52-month study

Over a 52-month period beginning in May 2004 and concluding in August 2008, and coinciding with the period over which TBT was banned as a ship anti-foulant globally, a population of the dogwhelk, Nucella lapillus, was studied for changes in population size and structure, and reproduction. During the study period, the size of the population of N. lapillus on the Mewsbrook Groyne at Littlehampton on the southeastern coast of England grew from ∼25 individuals to >500, i.e., a 20-fold increase. Similarly, population structure normalised to reveal a maximum age of up to ∼3 years. The numbers of egg capsules produced by the N. lapillus population also grew over the study, again by a factor of 20, and the length of the breeding season increased from 7 months in 2004-2005 and 2005-2006 to 11 months in 2006-2007 and 2007-2008. Such changes were reflected in the incidence of imposex from Vas Deferens Index Stages 3 and 4 in 2003 to zero commencing in 2008 and continuing into 2009.Due to a lack of confirmatory chemical data, the changes in population size, structure and reproduction herein reported upon for N. lapillus cannot be correlated positively with changes in ambient TBT levels, but they can and are correlated with freedom from imposex. This is the first time such a dramatic recovery from imposex, following the banning of TBT, has been documented.     

Anthropogenic influences on groundwater in the vicinity of a long‐lived radioactive waste repository

The groundwater flow system in the Culebra Dolomite Member (Culebra) of the Permian Rustler Formation is a potential radionuclide release pathway from the Waste Isolation Pilot Plant (WIPP), the only deep geological repository for transuranic waste in the United States. In early conceptual models of the Culebra, groundwater levels were not expected to fluctuate markedly, except in response to long‐term climatic changes, with response times on the order of hundreds to thousands of years. Recent groundwater pressures measured in monitoring wells record more than 25 m of drawdown. The fluctuations are attributed to pumping activities at a privately owned well that may be associated with the demand of the Permian Basin hydrocarbon industry for water. The unprecedented magnitude of drawdown provides an opportunity to quantitatively assess the influence of unplanned anthropogenic forcings near the WIPP. Spatially variable realizations of Culebra saturated hydraulic conductivity and specific storage were used to develop groundwater flow models to estimate a pumping rate for the private well and investigate its effect on advective transport. Simulated drawdown shows reasonable agreement with observations (average Model Efficiency coefficient = 0.7). Steepened hydraulic gradients associated with the pumping reduce estimates of conservative particle travel times across the domain by one half and shift the intersection of the average particle track with the compliance boundary by more than 2 km. The value of the transient simulations conducted for this study lies in their ability to (a) improve understanding of the Culebra groundwater flow system and (b) challenge the notion of time‐invariant land use in the vicinity of the WIPP.     

Field and large scale laboratory studies on dynamic properties of emplaced municipal solid waste from two dump sites at Delhi,India

Dynamic properties of municipal solid waste (MSW) from two dump sites located at Delhi, India are evaluated from field and large scale laboratory tests. Shear wave velocity (V_s) profiles of MSW, measured at these two sites using surface wave techniques, are in range of V_s data reported for MSW landfills worldwide. Representative bulk MSW samples were collected from large test pits excavated at the two dump sites to determine the near surface unit weight. Large scale undrained cyclic triaxial (CTX) tests were conducted on reconstituted MSW specimens to investigate the effect of various parameters such as composition, confining pressure, number of loading cycles, loading frequency and saturation on the dynamic properties. Undrained CTX tests, conducted on the specimens with and without fibrous materials demonstrated the effect of fibrous waste constituents on the stiffness and damping behavior of MSW. Specimens consisting of fibrous waste constituents such as plastics and textiles exhibited significantly less modulus reduction compared to specimens with negligible amount of fibrous content. The modulus reduction (G/G_max) and material damping ratio curves derived from the present study are in the range reported for MSW in the literature. The G/G_max curves from present study are in good agreement with curves recommended for MSW at Tri-Cities landfill in USA and Tianziling landfill in China. Dynamic properties evaluated from the present study add to the growing database of the worldwide dataset and can be useful for evaluating the seismic stability and associated permanent deformations of the existing dumps in and around Delhi.     

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.     

Structure-configurational entropy and its effect on the thermodynamic stability of uranyl phases: With special application for geological disposal of nuclear waste

Uranyl phases are found as the alteration products of uraninite under oxidizing condi- tions[1—3]. They are also expected to be the dominant alteration products of spent UO2 fuel in an oxidizing environment, such as at nuclear waste repositories[4—8]. …     

The performance of constructed wetlands for,wastewater treatment: a case study of Splash wetland in Nairobi Kenya

The performance of a constructed wetland for wastewater treatment was examined for four months (December 1995 to March 1996). The study area, hereby referred to as the Splash wetland, is approximately 0·5 ha, and is located in the southern part of Nairobi city. Splash wetland continuously receives domestic sewage from two busy restaurants. Treated wastewater is recycled for re‐use for various purposes in the restaurants. Both wet and dry season data were analysed with a view of determining the impact of seasonal variation on the system performance. The physical and chemical properties of water were measured at a common intake and at series of seven other points established along the wetland gradient and at the outlet where the water is collected and pumped for re‐use at the restaurants. The physico‐chemical characteristics of the wastewater changed significantly as the wastewater flowed through the respective wetland cells. A comparison of wastewater influent versus the effluent from the wetland revealed the system's apparent success in water treatment, especially in pH modification, removal of suspended solids, organic load and nutrients mean influent pH = 5·7 ± 0·5, mean effluent pH 7·7 ± 0·3; mean influent BOD₅ = 1603·0 ± 397·6 mg/l, mean effluent BOD₅ = 15·1 ± 2·5 mg/l; mean influent COD = 3749·8 ± 206·8 mg/l, mean effluent COD = 95·6 ± 7·2 mg/l; mean influent TSS = 195·4 ± 58·7 mg/l, mean effluent TSS = 4·7 ± 1·9 mg/l. As the wastewater flowed through the wetland system dissolved free and saline ammonia, NH₄⁺, decreased from 14·6 ± 4·1 mg/l to undetectable levels at the outlet. Dissolved oxygen increased progressively through the wetland system. Analysis of the data available did not reveal temporal variation in the system's performance. However, significant spatial variation was evident as the wetland removed most of the common pollutants and considerably improved the quality of the water, making it safe for re‐use at the restaurants. Copyright © 2001 John Wiley & Sons, Ltd.     

Towards an impact assessment of bauxite red mud waste on the knowledge of the structure and functions of bathyal ecosystems: The example of the Cassidaigne canyon (north-western Mediterranean Sea)

Since 1967, the alumina plants in the Marseilles area (Barasse and Gardanne) have been discharging the mineral residue (i.e., red mud) resulting from the alkaline processing of bauxite into the submarine Cassidaigne canyon (north-western Mediterranean Sea) through pipes situated at 320-330 m in depth. The Barasse pipe stopped being used in 1988. From 1987 to 1996, many decrees and regulations were promulgated by the French State to rule the conditions under which the Gardanne alumina refinery was authorized to dispose of the bauxite residue in the sea. The refinery was required: (i) to study the hydrodynamic circulation in the Cassidaigne canyon to evaluate the potential dispersion and transport of fine elements discharged into the water mass and their impact on the pelagic ecosystem; (ii) to survey the marine environment every five years to control the expansion and thickness of the red mud deposit and compare the evolution of the benthic macrofauna at representative sampling sites in the environment affected by the red mud discharge with that of reference sites outside of the red mud plume; (iii) to study the effect of the discharge on fishing activities; and (iv) to investigate the toxicity of the red mud, particularly its persistence, accumulation, interaction and effect on the marine ecosystem, paying special attention to the bio-accumulation of chromium and vanadium. A Scientific Committee was created to insure an independent evaluation of the studies promised by the manufacturer in response to the State’s regulations. Since the beginning of the 1960s, data have been accumulating on the structure and long-term functioning of the Cassidaigne bathyal ecosystem. This paper presents the collaborative efforts of the State-Manufacturer-Committee triplet and summarizes the main results obtained during the last period’s sea campaigns (1991-2007). This paper also illustrates how national regulations concerning manufacturers, such as Gardanne alumina refinery, have provided new knowledge about the structure and functioning of a bathyal ecosystem in the Cassidaigne canyon in the north-western Mediterranean Sea.