Antifouling biocides in discarded marine paint particles

Antifouling paint fragments collected from marinas and leisure boat maintenance facilities and in the vicinity of abandoned boats have been chemically characterised. High concentrations of Cu (23-380 mg g⁻¹) and Zn (14-160 mg g⁻¹) in the samples (n = 14) are consistent with the use of these metals in the principal biocidal and non-biocidal pigments in contemporary antifouling formulations. Up to about 2% and 7% of the respective metals were solvent-extractable, suggesting that organo-forms of Cu and Zn (e.g. pyrithiones) were also present. Of the organic biocides, dichlofluanid was present in most samples and at concentrations up to about 20 mg g⁻¹. Chlorothalonil and Irgarol 1051® were only detected in one and four cases, respectively, and Sea Nine 211® was not detected in any sample. Results are discussed in terms of UK legislation regarding biocide usage and the likely effects and fate of discarded paint particles in coastal environments where boats are repaired or moored.     

Antifouling biocides in water and sediments from California marinas

Irgarol 1051 is a common antifouling biocide and is highly toxic to non-target plant species at low ng/L concentrations. We measured up to 254 ng/L Irgarol in water and up to 9 ng/g dry weight Irgarol in sediments from Southern California recreational marinas. Irgarol’s metabolite, M1, concentrations were up to 62 ng/L in water and 5 ng/g dry weight in sediments. Another antifouling biocide, diuron, reached up to 68 ng/L in water and 4 ng/g dry weight in sediments. The maximum Irgarol concentrations in water were greater than the Irgarol concentration recommended as the plant toxicity benchmark (136 ng/L), suggesting that Irgarol concentrations may be high enough to cause changes in phytoplankton communities in the sampled marinas. Irgarol concentrations measured in sediments were greater than calculated Environmental Risk Limits (ERLs) for Irgarol in sediments (1.4 ng/g). Antifouling pesticide accumulation in sediments may present a potential undetermined risk for benthic organisms.     

Antifouling herbicides in the coastal waters of western Japan

Residue analyses of some antifouling herbicides (Diuron, Irgarol 1051 and the latter's degradation product M1, which is also known as GS26575), were conducted in waters collected along the coast of western Japan. In total, 142 water samples were collected from fishery harbours (99 sites), marinas (27 sites), and small ports (16 sites) around the Seto Inland Sea, the Kii Peninsula, and Lake Biwa, in August 1999. A urea-based herbicide, Diuron, was positively identified for the first time in Japanese aquatic environments. Diuron was detected in 121 samples (86%) up to a highest concentration of 3.05 microg/l, and was found in 86% of samples from fishery harbours, 89% from marinas, and 75% from ports. Four freshwater samples out of 11 collected at Lake Biwa contained Diuron. Neither Irgarol 1051 nor M1 was found in the lake waters, but both were found in many coastal waters. Irgarol 1051 was found in 84 samples (60%) at a highest concentration of 0.262 microg/l. The concentrations detected were of similar magnitude to those in our previous surveys, taken in 1997 and 1998. M1 was found in 40 samples (28%) up to a highest concentration of 0.080 microg/l. The concentrations detected were generally lower than those found in our previous surveys. The detection frequency among fishery harbours, marinas, and ports was 57-70% for Irgarol 1051 and 25-30% for M1. Ninety-five per cent of the coastal waters in which M1 was detected also contained Irgarol 1051, and 93% of the samples in which Irgarol 1051 was detected also contained Diuron. These results clearly suggest that commercial ship-bottom paints containing both Diuron and Irgarol 1051 are used extensively in the survey area.     

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.     

Antifouling activity of commercial biocides vs. natural and natural-derived products assessed by marine bacteria adhesion bioassay

Biofilm formation is a key step during marine biofouling, the natural colonization of immersed substrata, leading to major economic and ecological consequences. Consequently, bacteria have been used for the screening of new non-toxic antifoulants: the adhesion of five strains isolated on three French locations was monitored using a fluorescence-based assay and toxicity was also evaluated. Nine biocides including commercial, natural and natural-derived products were tested. The commercial antifoulants, TBTO and Sea Nine showed low EC₅₀ but high toxicity. The non-commercial products TFA-Z showed significant anti-adhesion activities and appeared to be non-toxic, suggesting a specific anti-adhesion mechanism. In addition, the strains could be classified depending on their sensitivity to the molecules used even if strain sensitivity also depended on the molecules tested. In conclusion, TFA-Z would be a promising candidate as non-toxic antifoulant and our results strengthen the need to perform antifouling bioassays with a panel of strains showing different response profiles.     

Probabilistic risk assessment of common booster biocides in surface waters of the harbours of Gran Canaria (Spain)

The presence of booster biocides in the aquatic environment has been associated with a risk to non-target species due to their proven toxicity. The aim of the present study was to determine the spatial and temporal distribution of common booster biocides in different harbours of the island of Gran Canaria (Spain) and evaluate, by means of a probabilistic risk assessment (PRA), the ecological risk posed by these compounds. With these objectives, a monitoring campaign was conducted between January 2008 and May 2009, collecting a total of 182 seawater samples. Four common booster biocides (TCMTB, diuron, Irgarol 1051 and dichlofluanid) were monitored. Diuron levels ranged between 2.3 and 203 ng/L and Irgarol 1051 between 2.4 and 146.5 ng/L. The ecological risk associated with these levels was always low, however, with probabilities of exceeding the 10th percentile of autotroph toxicity below 3.5%.     

Immediate industrial effects on sediment metals in a clean coastal environment

A programme to determine the immediate impact of a new nickel refinery on sediment metal levels in Halifax Bay, North Queensland was begun in May, 1975. The results indicate that within three weeks of the initiation of continuous refinery discharge to the Bay, area levels of at least one element (cobalt) had been significantly increased. In addition, samples taken from nearshore river mouth stations located near the plant also showed relatively high levels of nickel which may not be attributable to the plant's effluent discharge. The field data together with laboratory experiments suggest that future levels of cobalt, nickel and iron may be expected to increase significantly in Halifax Bay as a direct result of the refinery.     

Analyze the risks of biological invasion

Introducing non-native species can create serious environmental risks, such as changing the attributes of ecosystem, displacing the native species, clogging the natural waterways and channels. Careful examination of the possible consequences before implementation can prevent the adverse consequences of invasive species. However, policy analysis for such an action is often difficult, due to the complexity of the marine environment, and the interactions among the species therein.     

The effects of biological fouling control at coastal and estuarine power stations

The use of low levels of oxidants as antifouling agents in coastal and estuarine power station cooling water circuits can give rise to concerns over the likely production of chlorination byproducts (CBPs) including organohalogens, of largely cryptic identity, loading and impact. In order to review the current understanding of the degree of impact involved this paper describes a recent collaborative programme of work on CBPs within the wider context of a number of allied studies on power station cooling water entrainment and discharge effects. Bromoform was the single most important CBP found in coastal power station effluents. Although bromoform was found to accumulate in the liver of the sea bass Dicentrarchus labrax (L.) continuously exposed to a chlorinated effluent stream, no otherwise untoward impact on continuously exposed individuals was discerned. Populations of the common blue mussel Mytilus edulis L., likewise exposed, exhibited two responses: a high degree of genoplasticity and the evolution of stress proteins--although both may have been due to thermal rather than toxic stress. Experiments on plankton that simulated the conditions of entrainment within cooling water systems isolated the influence of oxidant usage, with mortality varying between taxa and life stage. The results suggest a very limited impact of oxidant use and the associated CBPs on receiving waters both in terms of plume toxicity or any more widespread ecotoxicological influence. Instead, it is in combination with applied temperature (DeltaT), pressure and the other stressors involved in entrainment within the power station cooling water circuits themselves that an impact is most marked.     

Immediate industrial effects on sediment mercury concentrations in a clean coastal environment

Studies were initiated in May 1975 to determine the impact of a new nickel refinery on ambient mercury level in sediments taken from Halifax Bay, Australia. Although mercury levels were relatively low in all samples, surface sediments were found to contain 2.5–3.0 times the mercury concentration of subsurface samples. However, surface sediment samples collected adjacent to the refinery outfall within the first three weeks of continuous discharge showed significant increases in mercury levels when compared with surface samples taken from areas not affected by the refinery.     

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.     

长江中下游地区湖泊沉积物杀生剂污染特征及生态风险

杀生剂作为抑菌活性成分,广泛应用于药物、个人护理品、食品、农业及其他多种领域中。大量杀生剂会直接或者随污水处理厂出水进入地表水环境中,威胁人体健康和生态安全。本研究通过对长江中下游地区61个湖泊进行调查,共检出11种杀生剂,包括5种杀菌剂、1种防污剂、3种尼泊金酯类防腐剂和2种消毒剂,总浓度达103 ng/g。其中,多菌灵和尼泊金甲酯的检出率大于50%,分别为100%和96.2%。多菌灵和尼泊金甲酯的平均浓度分别为（1.79±2.76）和（11.4±8.19） ng/g,其他杀生剂的平均浓度均低于1.0 ng/g。与国外许多河流湖泊相比,长江中下游地区湖泊沉积物中杀生剂污染处于中等偏低水平,总杀生剂浓度的平均值为（16.7±14.5） ng/g。氟康唑、咪康唑、三氯生和三氯卡班可能主要来自生活污水,多菌灵和涕必灵主要来自面源污染。尼泊金酯类防腐剂在沉积物中的分布特征与沉积物总有机碳含量密切相关。采用风险商值法对湖泊沉积物中杀生剂的生态风险进行了评价,发现多菌灵、尼泊金甲酯和三氯卡班在部分采样点具有高风险。有必要重点关注高风险污染物和高风险区域,并采取适当的措施来减少杀生剂对湖泊生态环境...     

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.     

Numerical modelling of the potential effects of a dam on a coastal aquifer in S. Spain

This study presents the results of a three‐dimensional variable‐density numerical modelling of the Motril‐Salobreña coastal aquifer and the possible effects of the entry into service in May 2005 of the Rules Dam, located just 17 km from the coast. Present parameters of the Motril‐Salobreña aquifer show that the system's conditions are very similar to a natural regime. The dam will substantially alter aquifer recharge, as the entry flow through the alluvial sediments of the Guadalfeo River will be entirely cut off or drastically reduced. Different scenarios reproducing the possible evolution of the aquifer under operation of the Rules Dam have been modelled. In most cases, results indicate that the conditions of the aquifer would worsen, with a general advance of the freshwater–saltwater interface. The area with most risk of saltwater intrusion is the old mouth of the Guadalfeo River, where the mixing zone could advance 1200 m inland. It is proposed that maintaining a 5–6 Mm³ year^?1 ‘ecological flow’ in the Guadalfeo River could prevent this saline advance. This application demonstrates that variable‐density models are potentially useful tools for estimating the effects of dams on the hydrodynamic and hydrochemical conditions of a coastal aquifer. Copyright © 2009 John Wiley & Sons, Ltd.     

Development of a fluorescent antibody method for the detection of Enterococcus faecium and its potential for coastal aquatic environment monitoring

A direct, microscopic fluorescent antibody method was developed to detect the occurrence of Enterococcus faecium in coastal aquatic environments and was compared with the conventional membrane filtering method. The "in situ" application of the antibody-based protocol in the analysis of water samples collected from coastal polyhaline habitats demonstrated good sensitivity and ease of implementation. Data obtained with the microscopic technique were in agreement with those obtained from culture counts. The fluorescent antibody method proved to be a rapid and reliable technique for the detection of E. faecium. The advantages and limitations intrinsic to the method are discussed, highlighting the potential of this new technique for monitoring coastal aquatic environments.     

Dissolved metal contamination in the East River-Long Island sound system: potential biological effects

A suite of dissolved trace metals (Ag, Cd, Cu and Pb), inorganic nutrients (NO(3), PO(4)), and chlorophyll a was measured along a 55 mile transect from the East River into western and central Long Island Sound. The main objectives of this study were to determine the relative levels of contamination from sewage, and to assess its possible biological impact on local waters. The East River-Long Island Sound system receives large volumes of treated sewage and industrial effluent as a result of the heavy urbanization of the area. Despite these strong environmental pressures, this study is among the first to report dissolved metal levels from that region. Consistent with the locations of anthropogenic sources, a strong east-west concentration gradient was observed for Ag, Pb, NO(3) and PO(4) with the highest levels found in the East River. In contrast, dissolved Cd and Cu were relatively constant throughout the area of study, suggesting that sewage sources have a more limited influence on the levels of those metals. Remobilization from contaminated sediments may represent the primary source of Cd and Cu to the Long Island Sound under low-runoff conditions in summer. Chlorophyll a concentrations, used as an indicator of total biomass, were also low in the East River. These low chlorophyll concentrations could not be explained by nutrient or light limitation, water column stratification, or to advection of phytoplankton out of the river during tidal flushing. These preliminary results suggest a potential toxic effect of sewage on the biological communities of the East River.