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.     

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.     

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.     

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.     

Organotin and Irgarol-1051 contamination in Singapore coastal waters

The seas surrounding Singapore are principally utilized by the shipping industry but are now also increasingly used for a variety of other purposes, including desalination for supplies of drinking water and intensive aquaculture of food fish. While stringent environmental pollution standards are in place for industrial effluents, there is currently no legislative control over pollution from anti-fouling paints in Singapore. In this study, the concentrations of toxic antifouling agents tributyltin (TBT), triphenyltin (TPhT) and Irgarol-1051 (2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine) were determined from seawater obtained from 26 locations along and off the coast of Singapore in October and November 2000. These compounds were isolated by liquid-liquid extraction derivatized under controlled microwave heating and quantified by gas chromatography-mass spectrometry. TBT concentrations in seawater ranged between 0.43 and 3.20 microg 1(-1) with a mean value of 1.40 +/- 0.60 micro 1(-1). The mean values of DBT and MBT were 1.07 +/- 0.80 microg 11(-1) and 0.34 +/- 0.50 microg 1(-1) respectively, while TPhT concentrations of up to 0.40 microg 1(-1) were found. Monophenyltin and diphenyltin were not detected in all samples analysed. Irgarol-1051 was found to be present at concentrations of between 3.02 microg 1(-1) and 4.20 microg 1(-1) in seawater with a mean value of 2.00 +/- 1.20 microg 1(-1).     

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.     

TBT toxicity on the marine microalga Nannochloropsis oculata

Commercial antifouling formulations containing TBT are the major source of organotin contamination in coastal waters. In view of the persisting TBT residues (13 ng Sn l⁻¹) in the coastal waters of South Korea, an attempt has been made to evaluate the growth response and biochemical composition of laboratory-cultured Nannochloropsis oculata to TBT toxicity. It is evident that the persisting concentration level of TBT is high enough to cause adverse effect on the microalgal species. The EC₅₀ (24 h) was found to be at 0.89 nM level of TBT for this marine eustigmatophyte N. oculata. Photosynthetic pigment content was significantly affected. At elevated TBT concentrations of 1.0 nM, especially pronounced changes in biochemical composition was found. TBT tolerance of N. oculata and its growth as well as biochemical responses are discussed.     

Biodegradation of petroleum products in experimental plots in Antarctic marine sediments is location dependent

Clean sediment collected from O'Brien Bay, East Antarctica, was artificially contaminated with a mix of Special Antarctic Blend diesel fuel and lubricating oil and deployed in two uncontaminated locations (O'Brien and Sparkes Bays) and a previously contaminated bay (Brown Bay) to evaluate whether a history of prior contamination would influence the biodegradation process. Detailed analysis of the hydrocarbon composition in the sediment after 11 weeks revealed different patterns of degradation in each bay. Biodegradation indices showed that hydrocarbon biodegradation occurred in all three bays but was most extensive in Brown Bay. This study shows that even within a relatively small geographical area, the longevity of hydrocarbons in Antarctic marine sediments can be variable. Our results are consistent with faster natural attenuation of spilt oil at sites with previous exposure to oil but further work is needed to confirm this. Such information would be useful when evaluating the true risk and longevity of oils spills.     

TBT toxicity on the marine microalga Nannochloropsis oculata

Commercial antifouling formulations containing TBT are the major source of organotin contamination in coastal waters. In view of the persisting TBT residues (13 ng Sn l⁻¹) in the coastal waters of South Korea, an attempt has been made to evaluate the growth response and biochemical composition of laboratory-cultured Nannochloropsis oculata to TBT toxicity. It is evident that the persisting concentration level of TBT is high enough to cause adverse effect on the microalgal species. The EC₅₀ (24 h) was found to be at 0.89 nM level of TBT for this marine eustigmatophyte N. oculata. Photosynthetic pigment content was significantly affected. At elevated TBT concentrations of 1.0 nM, especially pronounced changes in biochemical composition was found. TBT tolerance of N. oculata and its growth as well as biochemical responses are discussed.     

Understanding ship-grounding impacts on a coral reef: potential effects of anti-foulant paint contamination on coral recruitment

The 184 m cargo ship Bunga Teratai Satu collided with Sudbury Reef, part of the Great Barrier Reef and remained grounded for 12 days. The ship was re-floated only 3 days prior to the November 2000 mass coral spawning. No cargo or fuel was lost but the impact resulted in significant contamination of the reef with anti-foulant paint containing tributyltin (TBT), copper (Cu) and zinc (Zn). Larvae of the reef-building scleractinian coral Acropora microphthalma were exposed to various concentrations of sediment collected from the grounding site in replicated laboratory experiments. Two experiments were performed, both of which used varying ratios of contaminated and control site sediment in seawater as treatments. In the first experiment, the influence of contaminated sediment on larval competency was examined using metamorphosis bioassays. In the second, the effect of contaminated sediment upon larval recruitment on pre-conditioned terracotta tiles was assessed. In both experiments, sediment containing 8.0 mg kg(-1) TBT, 72 mg kg(-1) Cu and 92 mg kg(-1) Zn significantly inhibited larval settlement and metamorphosis. At this level of contamination larvae survived but contracted to a spherical shape and swimming and searching behaviour ceased. At higher contamination levels, 100% mortality was recorded. These results indicate that the contamination of sediment by anti-fouling paint at Sudbury Reef has the potential to significantly reduce coral recruitment in the immediate vicinity of the site and that this contamination may threaten the recovery of the resident coral community unless the paint is removed.     

Acute toxicities of five commonly used antifouling booster biocides to selected subtropical and cosmopolitan marine species

Since 1990s, various booster biocides have been increasingly used as substitutes of organotins. However, knowledge about their toxicities on tropical/sub-tropical marine species is significantly lacking. This study comprehensively investigated the acute toxicities of copper, tributyltin (TBT), and five commonly used booster biocides including Irgarol, diuron, zinc pyrithione (ZnPT), copper pyrithione (CuPT) and chlorothalonil on the growth or survival of 12 marine species in which eight of them are native species of subtropical Hong Kong. We found that Irgarol was more toxic than TBT on the growth of autotrophic species. The toxicity of CuPT was comparable to that of TBT on almost all test species, while it showed higher toxicity than TBT on medaka fish larvae. As the usage of these biocides is expected to further increase worldwide, accurate assessments of their ecological risks are required for better informed decision on their management. This study provided useful datasets for such purposes.     

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.     

基于远震接收函数的南极大陆冰盖厚度研究

冰盖厚度是研究南极冰盖质量、建立冰盖动力学模型的基本参数,对于冰川均衡调整、冰盖物质平衡及全球气候变化研究具有重要意义.基于地震学的远震接收函数和H-Kappa格网搜索方法可以用于地震台站下方冰盖厚度的可靠探测,不仅能与冰雷达获得的冰盖厚度进行独立对比,还可以与冰雷达方法相互补充,进一步填补南极大陆冰盖厚度探测空白区.本文利用布设于南极大陆冰盖上方的流动地震台阵记录到的远震波形数据,基于接收函数方法对台阵下方的冰盖厚度进行了研究.结果显示:基于远震接收函数方法的冰盖厚度与Bedmap2冰厚格网模型相比,二者差别大多在200 m以内;少数台站差值达到600 m左右,这一差别可能与Bedmap2测线分布空区、冰雷达测深不确定性以及冰盖内部复杂波速结构等因素有关.本文研究结果表明:利用南极大陆冰盖上方的流动地震台阵,基于远震接收函数方法可以获得比较可靠的南极冰盖厚度,为独立验证冰雷达的探测结果并弥补冰雷达探测空白区提供了有效方法.同时,部分台站接收函数波形的复杂性可能暗示了南极大陆数千米厚的冰盖内部结构不是均一的,仍然存在比较复杂的内部结构变化.因此,有必要进一步利用包括接收函数波形拟合、地震面波反演等方法对南极大陆冰盖厚度及其内部精细结构进行更为深入的研究.     

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.     

Coprostanols in Antarctic marine sediments: A biomarker for marine mammals and not human pollution

The first analysis of sterols in Antarctic marine sediment cores (Bransfield Strait and McMurdo Sound) is reported here. The isolated sterols in the sediments from Bransfield Strait are comprised mainly of dinosterol (4,23,24-trimethyl-5cholest-22-en-3β-ol), coprostanol (5β-cholestan-3β-ol) and epicoprostanol (5β-cholestan-3-ol) and trace amounts of cholesterol (cholest-5-en-3β-ol). The sediment cores of McMurdo Sound also contain small quantities of coprostanols in addition to large amounts of marine sterols. Dinosterol is a known dinoflagellate chemical marker, whereas coprostanols are currently being used as tracers for sewage contamination. However, sterol composition in Antarctic sediments is expected to be atypical of sewage input and probably different from those of temperate and tropical zones. The coprostanols must therefore arise from the feces of marine mammals, most probably whales which use the region for feeding and spawning. Based on the results of this study, caution should be exercised in the use of coprostanol to estimate the amount of sewage-derived organic matter transported away from impacted coastal areas.     

Trace elements in the sediments of a large Mediterranean marina (Port Camargue,France): Levels and contamination history

The study of trace elements (Cu, Zn, Pb, As, Hg) and butyltin concentrations in the sediments of Port Camargue enabled assessment of the levels and history of the contamination of the largest European marina linked with the use of antifouling paints. Surface sediments near the boat maintenance area were heavily contaminated with up to 1497 μg g⁻¹ of Cu, 475 μg g⁻¹ of Zn, 0.82 μg g⁻¹ of Hg, 94 μg g⁻¹ of Pb and over 10,000 ngSn g⁻¹ of tributyltin (TBT). High concentrations of Hg and TBT indicate ongoing sources of these elements despite the ban on their use as biocides in paints. Sediment cores provided records of contamination since 1969. The peak concentrations of As, Hg, Pb and TBT in the sediment profile reflect their presence on boat hulls when the marina was built at the end of the 1960s. Degradation of TBT in the sediments near the boat maintenance area is slow compared to other less contaminated area of the marina.     

Status of butyltin pollution along the coasts of western Japan in 2001, 11 years after partial restrictions on the usage of tributyltin

Restrictions on the use of tributyltin (TBT) in aquaculture and on boats in coastal regions, except for ocean-going vessels, have been in place in Japan since 1990 due to the strong toxic effects of TBT on marine organisms. However, TBT pollution along the Japanese coasts has been reported after this legislation was enacted. In order to elucidate the present status of contamination by butyltin (BT) compounds, we measured the levels of BTs [monobutyltin (MBT), dibutyltin (DBT) and TBT] in seawater and Caprella spp. samples obtained from the western part of Seto Inland Sea, Uwa Sea and Uranouchi Bay in western Japan during March to September, 2001. Butyltins were detected in more than 90% of the seawater samples (n = 59), with average concentrations of 8.2 ± 9.2 (SD) ng MBT L⁻¹, 3.3 ± 3.0 ng DBT L⁻¹ and 9.0 ± 7.0 ng TBT L⁻¹. Among 41 stations situated on coastal lines, a sufficient number of Caprella organisms for chemical analysis could be collected from only 16 stations. The butyltin concentrations in seawater and Caprella samples from Uwa Sea and Uranouchi Bay, in which the dominant industry in both waters is aquaculture, showed significantly higher than or no significant differences from those samples from the western part of Seto Inland Sea, a major heavy-industry area in Japan. As the TBT concentration in seawater increased, the number of Caprella organisms collected decreased. The mean TBT concentration among the seawater samples was above the estimated lowest observable effect concentration (LOEC) that reduces the survival rate of Caprella danilevskii. Thus, the present study indicates that TBT is still a potential ecological hazard to the survival of marine invertebrates inhabiting coasts along western Japan, even 11 years after the partial ban on TBT usage was implemented.     

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.     

The extent of hydrocarbon contamination in the marine environment from a research station in the Antarctic

Low level hydrocarbon contamination is measurable in the vicinity of Antarctic stations, N-alkane and polycyclic aromatic hydrocarbon (PAH) concentrations in seawater and sediment at Signy Station, South Orkney Islands indicated contamination was confined to within a few hundred metres of the station. Total n-alkane concentrations in seawater decreased from 7.6 to 2.6 μg l⁻¹ within 500 m of the station. All n-alkane values in seawater were within the limits of variation for oceanic waters proposed by cripps (1992), although the distribution pattern suggested pollution from the station. The total PAH concentration in seawater varied between 110 and 216 ng l⁻¹. These values showed no trend with distance from the station and were all slightly higher than for the open ocean. The n-alkane and PAH concentations in the surface sediment declined to low levels within 375 m of the station. This indicates that a large proportion of the hydrocarbons entering Factory Cove was deposited from the water column. Sediment n-alkane concentrations were similar at all depths of the cores when collected more than 125 m from the station. PAH levels in the sediment appeared to be due to local input, including a small spill in 1965.     

Tributyltin in blood of marine fish collected from a coastal area of northern Kyushu, Japan

We investigated levels of the pollutant tributyltin (TBT) in blood of pufferfishes (six species), Japanese sea perch, red sea bream, Japanese common goby, Japanese flounder, rockfish, conger eel, and sea mullet collected off the coast of northern Kyushu, Japan. We found considerable levels of TBT (1.4-190 ng/mL) accumulated in the blood of these fish. Blood TBT concentrations were 1.3-22.5 times liver concentrations and 4.9-78 times muscle concentrations, except in conger eel and mullet. We detected TBT (16-111 ng/mL-blood) in the plasma of the fine-patterned puffer (Takifugupoecilonotus) year-round, without any apparent seasonal trend. These results suggest that fish inhabiting coastal areas of Kyushu, Japan, continue to be contaminated with TBT.