梅承芳;梁慧君;周小翠;田亚静;邓桂荣;许玫英;栾天罡;曾国驱;

• 1:广东省微生物研究所
• 2:广东省菌种保藏与应用重点实验室
• 3:广东省微生物研究所
• 4:省部共建华南应用微生物国家重点实验室

摘要(Abstract)：

为有效控制防污漆中杀生物活性物质给海洋环境带来的不利影响,亟需开展活性物质的环境风险评估研究,为筛选环境友好型活性物质提供依据。以25种国产防污漆中的铜为评估对象,采用防污漆活性物质环境风险评估的针对性方法,分步进行暴露评估、危害性评估和风险表征。暴露评估采用海洋防污剂预测环境浓度模型(MAMPEC)中的港口、码头和开阔海域等典型暴露场景;危害性评估基于铜对淡水和海水水生生物的慢性毒性数据,采用物种敏感度分布法和评估因子法;风险表征采用熵值法。结果表明,铜对全部水生生物和海水生物的预测无效应浓度分别为2.8和2.3μg·L~(-1),藻类对铜最为敏感。除1种配方外,其余24种防污漆配方中铜的风险熵均小于1,可判定铜为"相对低风险"类活性物质,使用上述防污漆时铜对生态环境造成的风险较小。铜在不同暴露场景中的环境风险分析表明其对水流交换较弱海域的码头造成的风险最大,其次是默认港口和码头,对于公海造成的风险最小。根据现有的评估结果,设计含铜型防污漆配方时,应使铜的释放速率不大于33.5μg·cm~(-2)·d~(-1),以避免对较封闭海域的生态环境造成不可忽视的风险。

关键词(KeyWords)： 铜;海洋环境风险评估;防污漆活性物质;物种敏感度分布法;典型暴露场景;环境预测浓度;预测无效应浓度

Abstract:

Keywords:

基金项目(Foundation): 全球环境基金(GEF)中国用于防污漆生产的滴滴涕替代项目之环境保护领域化学品管理防污漆活性物质环境风险评估机构能力建设子项目;; 广东省海洋经济创新发展区域示范专项(No GD2012-D01-002);; 广东省科技计划项目(2013B090800004)

作者(Author): 梅承芳;梁慧君;周小翠;田亚静;邓桂荣;许玫英;栾天罡;曾国驱;

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参考文献(References)：

• [1]Champ M A.A review of organotin regulatory strategies,pending actions,related costs and benefits[J].Science of the Total Environment,2000,258:21–71
• [2]Voulvoulis N,Scrimshaw M D,Lester J N.Comparative environmental assessment of biocides used in antifouling paints[J].Chemosphere,2002,47:789–795
• [3]Almeida E,Diamantino T C,De Sousa O.Marine paints:The particular case of antifouling paints[J].Progress in Organic Coatings,2007,59:2–20
• [4]刘超,付玉彬,郑纪勇.环境友好型防污剂及海洋防污涂料的研究进展[J].材料开发与应用,2009,24(4):69–74Liu C,Fu Y B,Zhen J Y.Review on environmental friendly biocides and marine antifouling coatings[J].Development and Application of Materials,2009,24(4):69–74(in Chinese)
• [5]张春燕,于良民,姜晓辉,等.防污剂Sea–Nine211的环境归宿及其生态毒性研究进展[J].环境科学与技术,2010,33(2):107–111Zhang C Y,Yu L M,Jiang X H,et al.Progress in study of antifoulant sea-nine211:Fate in aquatic environment and its toxicity[J].Environment Science&Technology,2010,33(2):106-110(in Chinese)
• [6]黄运涛,彭乔.海洋生物污损的防治方法及研究进展[J].全面腐蚀控制,2004,18(1):3–5Huang Y T,Peng Q.The prevention method and research development of marine fouling[J].Total Corrosion Control,2004,18(1):3–5(in Chinese)
• [7]Takahashi K.Release rate of biocides from antifouling paints[J].Ecotoxicology of Antifouling Biocides,2009,1:3–22
• [8]Voulvoulis N,Scrimshaw M D,Lester J N.Occurrence of four biocides utilized in antifouling paints,as alternatives to organotin compounds,in waters and sediments of commercial estuary in the UK[J].Marine Pollution Bulletin,2000,11:938–946
• [9]Haglund K,Pettersson A,Pedersén M,et al.Seasonal distribution of the anti–fouling compound irgarol1051outside a marina in the Stockholm archipelago[J].Bulletin of Environmental Contamination and Toxicology,2001,66:55–58
• [10]Konstantinou I K,Albanis T A.Worldwide occurrence and effects of anti–fouling paint booster biocides in the aquatic environment:A review[J].Environment International,2004,30:235–248
• [11]Eklund B,Elfstrm M,Borg H.Tributyltin originates from pleasure boats in Sweden in spite of firm restrictions[J].Open Environmental Sciences,2008,2:124–132
• [12]Turner A.Marine pollution from antifouling paint particles[J].Marine Pollution Bulletin,2010,60:159–171
• [13]Ytreberg E,Karlsson J,Eklund B.Comparison of toxicity and release rates of Cu and Zn from anti–fouling paintsleached in natural and artificial brackish seawater[J].The Science of the Total Environment,2010,408:2459–2466
• [14]姜晓辉,于良民,董磊,等.新型防污剂异噻唑啉酮的衍生物的合成、生物毒性与防污性能研究[J].精细化工,2007,24(2):125–128Jiang X H,Yu L M,Dong L,et al.Synthesis and the toxicity and antifouling capability of new isothiazolinone derivatives[J].Fine Chemicals,2007,24(2):125–128(in Chinese)
• [15]姚宝书,冉庆云,陈万伦.辣椒碱自抛光防污涂料及其制备方法:中国专利,CN1477166[P].2004
• [16]梅承芳,陈进林,田亚静,等.防污漆中活性物质海洋环境风险评估关键技术探讨[J].生态毒理学报,2015,10(1):53–67Mei C F,Chen J L,Tian Y J.Review on recent approaches for marine environmental risk assessment of active substances in antifouling paints[J].Asian Journal of Ecotoxicology,2015,10(1):53–67(in Chinese)
• [17]王科,肖玲,于雪艳,等.防污剂对海洋环境的影响探讨[J].中国涂料,2010,25(8):24–30Wang K,Xiao L,Yu X Y,et al.Discussion on the influence of biocides on marine environment[J].China Coatings,2010,25(8):24-30(in Chinese)
• [18]Jones B,Bolam T.Copper speciation survey from UK marinas,harbours and estuaries[J].Marine Pollution Bulletin,2007,54(8):1127–1138
• [19]Matthiessen P,Reed J,Johnson M.Sources and potential effects of copper and zinc concentrations in the estuarine waters of Essex and Suffolk,United Kingdom[J].Marine Pollution Bulletin,1999,38:908–920
• [20]Schiff K,Diehl D,Valkirs A.Copper emission from antifouling paint on recreational vessel[J].Marine Pollution Bulletin,2004,48:371–377
• [21]Warnken J,Dunn R J K,Teasdale P R.Investigation of recreational boats as a source of copper at anchorage sites using time–integrated diffusive gradients in thin film and sediment measurements[J].Marine Pollution Bulletin,2004,49:833–843
• [22]Biggs T W,D’Anna H.Rapid increase in copper concentrations in a new marina,San Diego Bay[J].Marine Pollution Bulletin,2012,64:627–635
• [23]Matthiessen P,Reed J,Johnson M.Sources and potential effects of copper and zinc concentrations in the estuarine waters of Essex and Suffolk,United Kingdom[J].Marine Pollution Bulletin,1999,38:908–920
• [24]Schiff K,Brown J,Diehl D,et al.Extent and magnitude of copper contamination in marinas of the San Diego region,California,USA[J].Marine Pollution Bulletin,2007,54:322–328
• [25]US EPA.Summary review of the health effects associated with copper[R].Cincinnati:Health issue assessment,1987
• [26]Andersson S,Kautsky L.Copper effects on reproductive stages of Baltic Sea Fucus vesiculosus[J].Marine Biology,1996,125:171–176
• [27]Hall L W,Anderson R D.A deterministic ecological risk assessment for copper in European saltwater environments[J].Marine Pollution Bulletin,1999,38:207–218
• [28]Nadella S R,Fitzpatrick J L,Franklin N,et al.Toxicity of dissolved Cu,Zn,Ni and Cd to developing embryos of the blue mussel(Mytilus trossolus)and the protective effect of dissolved organic carbon[J].Comparative Biochemistry and Physiology C,2009,149:340–348
• [29]Katranitsas A,Castritsi–Catharios J,Persoone G.The effects of a copper–based antifouling paint on mortality and enzymatic activity of a non–target marine organism[J].Marine Pollution Bulletin,2003,46:1491–1494
• [30]Singh N,Turner A.Leaching of copper and zinc from spent antifouling paint particles[J].Environmental Pollution,2009,157:371–376
• [31]Bao V W W,Leung K M Y,Kwok K W H,et al.Synergistic toxic effects of zinc pyrithione and copper to three marine species:Implications on setting appropriate water quality criteria[J].Marine Pollution Bulletin,2008,57:616–623
• [32]European Copper Institute.Voluntary risk assessment reports–copper and copper compounds[EB/OL].Belgium:ECI,2008.http://www.echa.europa.eu/web/guest/copper–voluntary–risk–assessment–reports?search_criteria=7440–50–8,2013
• [33]王增焕,林钦,李刘冬,等.大型海藻对重金属镉、铜的富集动力学研究[J].中国环境科学,2013,33(1):154–160Wang Z H,Lin Q,Li L D,et al.Kinetic study on the bioconcentration of cadmium and copper by large-sized seaweed Gracilaria lemaneiformis[J].China Environmental Science,2013,33(1):154–160(in Chinese)
• [34]ISO.ISO 13073–1,Ship and marine technology–Risk assessment on anti–fouling systems on ships–Part 1:Marine environmental risk assessment method of biocidally active substances used for anti–fouling systems on ships[S].2012
• [35]European Commission.Technical Guidance Document on Risk Assessment,Part II[R].Italy:Euroean Chemicals Bureau(ECB)JRC–Ispra(VA),2003
• [36]ISO.ISO 10890 Paints and varnishes–Modelling of biocide release rate from antifouling paints by mass–balance calculation[S].2010
• [37]Turner A.Trace–metal partitioning in estuaries:Importance of salinity and particle concentration[J].Marine Chemistry,1996,54:27–39
• [38]Klimisch H J,Andreae M,Tillmann U.A systematic approach for evaluating the quality of experimental toxicological and ecotoxicological data[J].Regulatory Toxicology and Pharmacology,1997,25:1–5
• [39]Van Hattum B,Baart A D,Boon J G.Computer model to generate predicted environmental concentrations(PECs)for antifouling products in the marine environment[M/OL].Amsterdam:IVM,2002.http://www.deltares.nl/en/software/1039844/mampec/1232327,2013
• [40]王振,金小伟,王子健.铜对水生生物的毒性:类群特异性敏感度分析[J].生态毒理学报,2014,9(4):640–646Wang Z,Jin X W,Wang Z J.Taxon-specific sensitivity differences of copper to aquatic organisms[J].Asian Journal of Ecotoxicology,2014,9(4):640–646(in Chinese)
• [41]Hutchinson T H,Scholz N,Guhl W.Analysis of the ecetoc aquatic toxicity(EAT)database IV-Comparative toxicity of chemical substances to freshwater versus saltwater organisms[J].Chemosphere,1998,36(1):143–153
• [42]吴丰昌,冯承莲,曹宇静,等.我国铜的淡水水生水质基准研究[J].生态毒理学报,2011,6:617–628Wu F C,Feng C L,Cao Y J,et al.Aquatic life ambient freshwater quality criteria for copper in China[J].Asian Journal of Ecotoxicology,2011,6:617–628(in Chinese)
• [43]Thomas K,Raymond K,Chadwick J,et al.The effects of short–term changes in environmental parameters on the release of biocides from antifouling coatings:Cuprous oxide and tributyltin[J].Applied Organometallic Chemistry,1999,13:453–460
• [44]Valkirs A O,Seligman P F,Haslbeck E,et al.Measurement of copper release rates from antifouling paint under laboratory and in situ conditions:Implications for loading estimation to marine water bodies[J].Marine Pollution Bulletin,2003,46:763–779
• [45]Finnie A A.Improved estimates of environmental copper release rates from antifouling products[J].Biofouling,2006,22(5–6):279–291