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1.
The release of biocides, such as copper (Cu), from antifouling (AF) coatings on vessel hulls represents a significant proportion of overall Cu loading in those harbors and estuaries where substantial numbers of small craft or large vessels are berthed. Copper release rates were measured on several self-polishing, tin-free coatings and an ablative Cu reference coating applied to steel panels using three measurement methods. The panels were exposed in natural seawater in San Diego Bay, and release rates were measured both in the laboratory and field over 2 years. Results with the static (20 cm x 30 cm) panels indicated that Cu release rates were initially high (25-65 microg Cu cm(-2)day(-1)), with a large range of values between paint types. Release rates declined to substantially lower rates (8-22 microg cm(-2)day(-1)) with reduced variability within 2 months. Release rates continued to decrease over time for approximately 6 months when relatively constant release rates were observed for most coatings. Over time, relative differences in Cu release rates measured by three exposure methods decreased, with all coatings exhibiting similar behavior toward the end of the study. Lowest overall Cu release rates were observed with the self-polishing experimental paint no. 7 in static-dynamic and in situ treatments. The highest periodic release rates were measured from panels that experienced periods of both static and dynamic exposure (8.7 ms(-1) rotation). The lowest release rates were measured from panels that experienced static, constant depth exposure, and where release rates were evaluated in situ, using a novel diver-deployed measurement system. Results from this in situ technique suggests that it more closely reflects actual Cu release rates on vessel hulls measured with intact natural biofilms under ambient conditions than measurements using standardized laboratory release rate methods. In situ measurements made directly on the AF surface of vessels demonstrated typically lower release rates than from the panel studies, averaging 8.2 microg cm(-2)day(-1) on pleasure craft, and 3.8 microg cm(-2)day(-1) on Navy vessels. The data suggest that the presence of an established biofilm likely serves to moderate the release of Cu from field-exposed antifouling coatings both on panels and hull surfaces. 相似文献
2.
The use of copper in antifouling paints has increased in the UK in the last 20 years as TBT and several other organic biocides have been phased out. To assess the probable impact of copper on estuarine systems a survey was undertaken to measure the different fractions of copper present in the water column at current usage. The different fractions measured were; labile copper, (LCu) considered as both the free copper ions and inorganically bound copper, the total dissolved copper (TDCu) present, and the difference between them taken as the organically bound likely non-toxic copper fraction. The survey considered sites with different levels of boat use, namely marinas, harbours and estuaries, differing physical parameters of suspended and dissolved organic matter, different seasons of the year and different depths in the water column all of which control speciation behaviour. Suspended particulate matter (SPM) values were measured at all sites and increased from West to East coast locations (5.7-34.4 mg/l). Dissolved organic matter (DOM) values ranged from 0.58 to 2.2mg/l C. The total dissolved copper concentrations ranged from 0.30 to 6.68 microg/l, with labile fraction ranging from 0.02 to 2.69 microg/l, and most labile copper concentrations below 1 microg/l. None of the yearly mean copper measurements exceeded the 76/464/EEC EQS of 5 microg/l. Of the 306 measurements, only one dissolved copper value in one season was above 5 microg/l. This ratio of labile to total copper was between 10 and 30%. The results from this survey suggest that if toxicity of copper is due to the labile fraction then using the total dissolved copper concentrations as an indicator of impact overestimate the risk by a factor of four times. 相似文献
3.
Jones RJ 《Marine pollution bulletin》2007,54(7):905-911
Bulk metal analyses of surficial sediments collected around the Norwegian Crown cruise ship grounding site in Bermuda indicated significant but localized contamination of reef sediments by copper and zinc, caused by the stripping of the tri-butyltin (TBT)-free antifouling (AF) paint (Intersmooth 460) from the underside of the hull. Highest copper and zinc values were found in heavily compacted and red-pigmented sediments inside the impact scar and were comparable to levels found close to slip ways of local boat yards where AF paints from hull stripping and cleaning processes are washed into the sea. The re-distribution of AF contaminated sediments by storms and deposition on nearby reefs constitutes a significant ecological risk that could delay recovery processes and reduce the effectiveness of remediation efforts. Whilst the ecotoxicological effects of AF paint particles interspersed with sediment is unknown, and in need of further study, it is argued that the significance of AF paint contamination of grounding sites has been overlooked. 相似文献
4.
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. 相似文献
5.
Environmental hazards associated with traditional, toxic antifouling coatings based on heavy metals calls for the development of alternative, environmentally acceptable antifouling compounds. Medetomidine ((±)-4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole) is a candidate antifouling biocide which impedes settlement of barnacles in the nanomolar range. Prior to introducing novel biocides it is of great importance to consider potential effects on non-target organisms. This study is the first to investigate the effects of medetomidine on the amphipod Corophium volutator, specifically effects on male mate search behaviour. In a laboratory, Y-maze bioassay, C. volutator males were allowed to follow female pheromones after 24 h exposure to 0 (control), 0.01 and 0.1 μg mL−1 medetomidine. We found that exposure to medetomidine at both concentrations significantly reduced pheromone induced mate search (by 42–71%), with fewer males crawling towards female odour. The results obtained indicate that medetomidine may impair the reproductive fitness of non-target crustaceans, an aspect that needs to be considered before further commercialisation. 相似文献
6.
Marinas are areas of special water quality concern because of the potential for pollutant accumulation within their protected waters. Perhaps the largest contaminant source to marinas is antifouling paints that leach copper to prevent the growth of encrusting organisms on vessel bottoms. Very little monitoring of marinas is typically conducted despite the potential environmental risk, particularly in the San Diego region of California, USA where as many as 17,000 recreational vessels are berthed. The objective of this study was twofold: (1) determine the extent and magnitude of dissolved copper concentrations in marinas throughout the San Diego region, and (2) determine if elevated copper concentrations in marinas of the San Diego region are resulting in adverse biological impacts. A probabilistic study design was used to sample water column copper concentrations and toxicity (using Mytilus galloprovincialis) at 30 stations. Results indicated that exceedence of state water quality objectives was widespread (86% of marina area), but that toxicity was much less prevalent (21% of marina area). Toxicity identification evaluations (TIEs) conducted at the most toxic sites indicated that toxicity was largely due to trace metals, most likely copper. Toxicity was reduced using TIE treatments that chelated trace metals such as cation exchange column, ethylenediaminetetraacetic acid (EDTA), and sodium thiosulfate (STS). Moreover, increasing dissolved copper concentrations correlated with increasing toxicity and these copper concentrations were high enough to account for virtually all of the observed toxicity. 相似文献
7.
Abdellatif Mellouki Armand Bianchi Alain Perichaud Georges Sauvet 《Marine pollution bulletin》1989,20(12):612-615
The most common way to prevent biofouling of immersed surfaces is to coat the exposed surfaces with a paint containing a biocide acting on marine organisms by diffusion into the surrounding water. However diffusion of toxins into the marine environment causes pollution and serious economic problems. This paper outlines the anti-microfouling properties of some insolubilized quaternary ammonium salts (grafted onto a vinyl copolymer by means of a covalent non-hydrolyzable bond). After immersion times in sea-water up to 4 months, the microbial cover was limited to bacterial forms, without microalgae or cyanobacteria as observed on the untreated, or tin-salt painted surfaces. Bacteria are mostly on unicell forms and numerous areas appear free of any microorganisms. As microbiofouling is an obligate step to macrofouling, this unleachable antifouling treatment could result in a prolonged protection. 相似文献
8.
Zinc pyrithione (ZnPT) is widely applied in conjunction with copper (Cu) in antifouling paints as a substitute for tributyltin. The combined effects of ZnPT and Cu on marine organisms, however, have not been fully investigated. This study examined the toxicities of ZnPT alone and in combination with Cu to the diatom Thalassiosira pseudonana, polychaete larvae Hydroides elegans and amphipod Elasmopus rapax. Importantly, ZnPT and Cu resulted in a strong synergistic effect with isobologram interaction parameter lambda>1 for all test species. The combined toxicity of ZnPT and Cu was successfully modelled using the non-parametric response surface and its contour. Such synergistic effects may be partly due to the formation of copper pyrithione. It is, therefore, inadequate to assess the ecological risk of ZnPT to marine organisms solely based on the toxicity data generated from the biocide alone. To better protect precious marine resources, it is advocated to develop appropriate water quality criteria for ZnPT with the consideration of its compelling synergistic effects with Cu at environmentally realistic concentrations. 相似文献
9.
The paper discusses active and passive methods of reducing the expected oil outflow from collision and grounding accidents. Active measures refer to actions or decisions taken at the time of an accident, while passive measures refer to features built into the design of the ship. Except in cases of large tides, passive measures appear most efficient in reducing the oil spill rates from collision and grounding accidents. The measures discussed in this study include:
• • main hull design and tank arrangement;
• • structural resistance of hull; and
• • other features, like vacuum systems, piping systems for automatic redistribution of oil in case of pressure drop in tanks.
Only the influence of the main hull design and tank arrangement on the oil outflow has been analysed in detail. A probabilistic outflow model, which simulates damage cases in accordance with observed data from collision and grounding accidents, has been used for a parameter study of the oil spills from a double hull tanker of 280 000 DWT. This has established the optimum position of longitudinal bulkheads to minimize the outflow rates, the variation of the outflow volumes with tank length (number of oil tanks) and the effect of altering main particulars or hull slenderness on outflow rates. Further simplified models are used to assess how these variations in main hull design and tank arrangement will affect the steel weights and associated costs of the analysed designs. The results reveal that a considerable reduction of the pollution risk may be achieved by careful modification of main particulars and tank sizes compared to current design practice. 相似文献
10.
In 2001, legislative measures were introduced in the UK to restrict usage of antifouling agents in small (<25 m) vessel paints to dichlofluanid, zinc pyrithione and zineb. This removed the previously popular booster biocides diuron and Irgarol 1051 from the market. To investigate the impact of this legislation, water samples were taken from locations where previous biocide levels were well documented. Results from analyses demonstrate a clear reduction in water concentrations of Irgarol 1051 (between 10% and 55% of that found during pre-restriction studies), indicating that legislation appears to have been effective. Although other booster biocides were screened for (chlorothalonil, dichlofluanid and Sea-Nine 211), they were below the limits of detection (<1 ng/l) in all samples. A survey of chandlers and discussions with legislative authorities supports these results and concurs the removal of Irgarol 1051 based paints from the market using simple regulations at a manufacturer level with little regulation at a retailer level. 相似文献
11.
Environmental impacts of vessels are well documented; Cu pollution as result of Cu based antifouling paints and nutrient pollution (such as N) from marine sewage are two examples of such disturbances. Understanding environmental impacts as well as the use of coastal waterways by recreational vessels is of concern to regulatory authorities, waterway users and local residents. In this study more than 55 aerial surveys were conducted of selected popular anchorages in eastern Moreton Bay, Queensland, Australia. Numbers of recreational vessels at certain times during the year were used in multiple linear regression analyses to develop predictive models for recreational vessel numbers. Over one year approximately 10,000 locally registered recreational craft (>6m length overall) generated an estimated 59,000 vessel nights. With Cu leaching rates from the literature, and estimates of sewage inputs (assuming little or no use of pump-out facilities), load estimates associated with overnight use of 20 popular anchor sites were calculated as 141+/-46 kg of Cu and 1.17+/-0.38 t of nitrogen (N) annually. More importantly, the models showed vessel activity to be highly variable, and focused at peak holiday times, with 14% of vessel activity and associated pollutant loads entering the environment during Christmas and Easter. This study highlighted the inherent difficulties in managing a popular maritime amenity and Marine Parks such as the Moreton Bay Marine Protected Area, Queensland, Australia with its variety of stakeholders and types and intensities of uses. 相似文献
12.
A study on the treatment of antifouling paint waste from shipyards, including sandblast waste and ship hull washing wastewater, was performed. The sandblast waste could be effectively detoxified by heat treatment, and the efficiency was affected by the temperature of the heating vessel and treatment time. The removal efficiency of total organotin compounds from the sandblast waste was over 99% at 1000 °C and treatment for 1 h. For the treatment of ship hull washing wastewater by the solvent extraction, ship diesel was a good solvent for the tributyltin (TBT) extraction, and the proper amount of solvent was about 10 mL for TBT extraction from 1 L of wastewater. The extraction efficiency of TBT was significantly affected by the agitation intensity. The TBT in the wash wastewater was rapidly extracted within 1 h. The level of the TBT residual in the wastewater extracted for 1 h was 2.8 μg L−1, and this was further decreased to 0.8 after 5 h extraction. 相似文献
13.
《Marine pollution bulletin》2009,58(6-12):616-623
Zinc pyrithione (ZnPT) is widely applied in conjunction with copper (Cu) in antifouling paints as a substitute for tributyltin. The combined effects of ZnPT and Cu on marine organisms, however, have not been fully investigated. This study examined the toxicities of ZnPT alone and in combination with Cu to the diatom Thalassiosira pseudonana, polychaete larvae Hydroides elegans and amphipod Elasmopus rapax. Importantly, ZnPT and Cu resulted in a strong synergistic effect with isobologram interaction parameter λ > 1 for all test species. The combined toxicity of ZnPT and Cu was successfully modelled using the non-parametric response surface and its contour. Such synergistic effects may be partly due to the formation of copper pyrithione. It is, therefore, inadequate to assess the ecological risk of ZnPT to marine organisms solely based on the toxicity data generated from the biocide alone. To better protect precious marine resources, it is advocated to develop appropriate water quality criteria for ZnPT with the consideration of its compelling synergistic effects with Cu at environmentally realistic concentrations. 相似文献
14.
An integrated approach including chemical speciation analyses and microalgal bioassays was used to assess the impact of copper from copper mining on a coastal area in Northern Chile. Dissolved copper ranged from <1 microg l(-1) at reference sites to 48 microgl(-1) at sites close to the mine discharge. Dissolved copper at sites closest to the discharge always exceeded seawater complexing capacities determined by anodic stripping voltammetry (ASV), and consequently labile copper was always detected (1-37 microg l(-1)). Agreement between ASV-labile copper and copper retained by cation exchange (ALSA) columns was excellent. Measured labile copper also accurately predicted bioavailable copper determined by growth inhibition of Nitzschia closterium and enzyme inhibition in Dunaliella tertiolecta. Seawater from Caleta La Lancha had the highest dissolved and labile copper and was the most toxic to micro-algal growth and enzyme activity. Previous studies at this site confirmed it had the lowest level of biodiversity, suggesting that copper may have both direct and indirect effects on these communities. 相似文献
15.
淀山湖底泥生态疏浚适宜深度判定分析 总被引：3，自引：3，他引：0
通过室内模拟实验,对淀山湖东部湖区的沉积物进行研究,测定沉积物在不同疏浚深度和疏浚温度下的铵态氮(NH4+-N)、正磷酸盐(NH43--P)和溶解性有机碳(DOC)的释放速率,并对该区域沉积物的理化指标进行检测.结果表明:淀山湖表层沉积物近年来总磷和有机质含量有较大增加.淀山湖东部湖区NH4+-N和DOC存在着释放趋势,NH43--P在夏季会从沉积物中向上覆水中释放,在年内会形成"源"和"汇"的转化.整个淀山湖东部湖区按不同研究区域划分,疏浚深度以10~20 cm最佳,疏浚季节以秋季为佳.通过对淀山湖东部湖区的沉积物在不同疏浚深度和疏浚时间下的污染物释放速率的研究,可以为淀山湖和其它类似湖泊的疏浚工作提供相应的科学依据. 相似文献
16.
Medina M Andrade S Faugeron S Lagos N Mella D Correa JA 《Marine pollution bulletin》2005,50(4):396-409
Copper mine tailings have been discharged around the city of Chanaral, in northern Chile, for more than 60 years. This report summarizes a 17-month long monitoring study of species richness and biodiversity at five intertidal sites around the point of the tailing discharge. Total dissolved copper in sites close to the point of discharge varied between 8.72 microg/l and 34.15 microg/l, showing that there has not been a significant reduction since 1994. However, species richness has increased, suggesting a possible recovery of the system. While diversity of sessile organisms correlates negatively with dissolved copper, diversity of mobile invertebrates did not correlate with the metal concentration. To explain the observed results we discuss the role of algal turf interference on the distribution of mobile invertebrates at reference sites, a top-down effect caused by the absence of carnivores at impacted sites, and an avoidance strategy by some species to reduce their contact with contaminated seawater. 相似文献
17.
《Marine pollution bulletin》2009,58(6-12):838-845
Environmental impacts of vessels are well documented; Cu pollution as result of Cu based antifouling paints and nutrient pollution (such as N) from marine sewage are two examples of such disturbances. Understanding environmental impacts as well as the use of coastal waterways by recreational vessels is of concern to regulatory authorities, waterway users and local residents. In this study more than 55 aerial surveys were conducted of selected popular anchorages in eastern Moreton Bay, Queensland, Australia. Numbers of recreational vessels at certain times during the year were used in multiple linear regression analyses to develop predictive models for recreational vessel numbers. Over one year approximately 10,000 locally registered recreational craft (>6 m length overall) generated an estimated 59,000 vessel nights. With Cu leaching rates from the literature, and estimates of sewage inputs (assuming little or no use of pump-out facilities), load estimates associated with overnight use of 20 popular anchor sites were calculated as 141 ± 46 kg of Cu and 1.17 ± 0.38 t of nitrogen (N) annually. More importantly, the models showed vessel activity to be highly variable, and focused at peak holiday times, with 14% of vessel activity and associated pollutant loads entering the environment during Christmas and Easter. This study highlighted the inherent difficulties in managing a popular maritime amenity and Marine Parks such as the Moreton Bay Marine Protected Area, Queensland, Australia with its variety of stakeholders and types and intensities of uses. 相似文献
18.
The effects of a copper-based antifouling paint on mortality and enzymatic activity of a non-target marine organism 总被引：2，自引：0，他引：2
Antifouling paints are used on a wide range of underwater structures in order to protect them from the development of fouling organisms. The leaching of the toxic substances from the matrix of the paint causes toxic effects not only to the fouling organisms but also on other "non-target" biota. The present study addresses the impact of the antifouling paint Flexgard VI-II on brine shrimp nauplii selected as convenient test organisms. The surface to volume (S/V) concept developed by Persoone and Castritsi-Catharios (1989) was used to determine S/V-LC50s for the test biota exposed to PVC test panels of 400-1000 mm2 surface coated with the antifouling paint in test vessels containing 20 ml seawater. Total ATPase and Mg2+-ATPase were also analyzed for coated surface areas inducing less than 50% mortality in the brine shrimp nauplii. The calculated S/V-LC50 (24 h) was 24.6 mm2/ml, which shows the high toxic character of the antifouling paint. Decreased enzymatic activities were noted in the brine shrimp nauplii exposed to test panels of 50 and 100 mm2 in 20 ml seawater. The present study indicates that the "surface to volume" concept is an interesting methodology that can be applied with both lethal and sublethal effect criteria for the determination of toxic stress from leaches of painted surfaces. 相似文献
19.
The radiocarbon age profile of a sediment core from the eastern equatorial Atlantic shows a marked decrease in both clay and carbonate accumulation rates at the end of the last glacial period, with overall rates of 3.2 and 8.1 cm/kyr for the Holocene and late glacial respectively. The transition from glacial to postglacial conditions recorded in the sediments at 39 cm is above the visual Fe(II)/Fe(III) redox boundary at 48 cm which has been used in the past to identify the glacial section, and even further above the increase in preserved organic carbon content at 55 cm. It is concluded from the present organic carbon profile, and recent observations in this area and elsewhere, that organic diagenesis in these sediments is not steady state. Instead it is suggested that the uppermost glacial sediments lost carbon through oxic remineralisation at the change to postglacial conditions, and that this process is now continued with nitrate as the electron acceptor. These observations suggest that the double MnOx solid phase peak which occurs in these and similar sediments is a direct consequence of an adjustment of the oxic layer depth following the decrease in carbon flux at the onset of the Holocene. 相似文献
20.
Yuyuan Li Ru Gao Rui Yang Hongan Wei Yong Li Heai Xiao Jinshui Wu 《洁净——土壤、空气、水》2013,41(11):1100-1107
The impacts of soil P leaching on water eutrophication have widely been concerned. However, there is no dependable method to quantitatively estimate the P leaching risk of soils. In this study, a simple soil column method was developed using two calcareous Fluvisols, silt loam and loam. The soil column was 20 cm in length and 5 cm in diameter, and distilled water was continuously supplied from the top. The volume and dissolved reactive P (DRP) concentrations of leachate were measured. Results showed that DRP concentrations in leachate increased slowly for the low soil Olsen‐P levels but rapidly for the high Olsen‐P levels. According to these two‐phase changes in the DRP versus soil Olsen‐P contents, the thresholds of P leaching risk were estimated to be 41.1 and 62.3 mg P kg?1 (Olsen‐P) for silt loam and loam, respectively. The P leaching intensity of soils increased by 3‐ to 540‐fold if the soil Olsen‐P contents accumulated from 6.6 to 155.5 mg P kg?1. The outcomes derived from this study regarding the determination of P leaching threshold and intensity by the soil column method also need a further verification on more soils with a wide range of physical and chemical properties. 相似文献