Research On Methods Of Detecting Typical Antifouling Agents And Evaluation Of Eco-toxicity Of Marine Antifouling Paints

With the development of marine scientific research and ocean economy, marineantifouling technology was also developed. The use of marine antifouling coatingscan effectively prevent the adhesion of marine fouling, reducing the cost ofmaritime transportation and other expenses. However, marine antifouling coatingswere not only kill marine fouling organisms, but also for some non-target organismsand even entire marine ecosystems have had a serious impact.Marine paint antifouling agent added are bad for marine organism, they cancause a variety of biological variation, endangering the stability of the marine foodchain, damage to the marine ecological balance, and thus pose a threat to humanhealth. Currently, in China, the detection method of hazardous material in marinecoatings is not perfect. EU standards is used to determine content of paints bymeasuring the heavy metal content of pesticides profile at home, but this method hasa big error that it’s difficult to distinguish the true ingredients of pesticides. Andbased on the existing decoration materials GB18581and GB18582standards fortesting, it is difficult to control the harmful pesticides in marine coatings, and it doesnot serve the purpose of protecting the environment. Based on this, the GC-MS andHPLC methods for the determination of7kinds of antifouling biocides(chlorothalonil, dichlofluanid, Sea-Nine211, Irgarol1051, diuron, ZPT and CPT)and risk analysis model in marine coatings have been developed in this paper, andthe acute toxicity of the marine antifouling coatings are evaluated. In addition, atoxicity index of marine paint was applied to the environmental risk model forgraded the relative toxicity of marine antifouling coatings.The conclusions in this thesis are included as follows:1. The GC-MS method and HPLC method for the determination of7kinds of antifouling biocides in marine coatings have been developed. Procedure of samplepre-treatment and condition of instruments was optimized. Under such optimizedconditions, the recovery range was varied from82.6%~109.9%, the relativestandarddeviations were less than4%. In the concentration range, the linearrelationship of the method was very well and correlation coefficients was greaterthan0.99.2. The newly presented method of risk analysis uses release rate, spatiotemporalrange, bioaccumulation, biological activity and remaining uncertainty as5dimensions of ecotoxicoloical risk. For each dimension, a procedure is brieflydescribed. Based on this, the qualitative model of risk analysis of antifouling agentwas established. The resulting risk profiles of the antifouling biocides showcharacteristics of the different substances, but also indicate where furter informationis required. According to the qualitative model of risk analysis, antifouling agentscan be characterized by the clustering intuitive map.3. Acute toxicities of marine antifouling coatings are determined to fivespecies representing different phyla occupying a wide range of niches: Skeletonemacostatum, Prorocentrum minimum, Amphidinium carterae Hulburt, Artemia andDanio rerio. Organisms are exposed to static antifouling coating concentrations for96h, then median lethal concentration (LC50) and median effect concentration (EC50)were calculated. Based on LC50and EC50values, we can know that phyplanktonSkeletonema costatum is the most sensitive species. In addition, Skeletonemacostatum is primary producer of the main marine food chain, which also widelydistributed and easily gain. Therefore, we can recommend the most sensitive speciesSkeletonema costatum as the best aquatic test organism to evaluate the toxicityeffects of antifouling coatings to marine environment.4. In this paper, environmental risk model was estiblished, a toxicity index ofantifouling paints (ATI) and comprehensive release index (CRI) were applied to theenvironmental risk model for graded the relative toxicity of marine antifoulingcoatings.The innovation in this thesis are included as follows: 1. The GC-MS method for the determination of4kinds of antifouling biocides(chlorothalonil, dichlofluanid, Sea-Nine211and Irgarol1051) and the HPLCmethod for the determination of diuron, ZPT and CPT in marine coatings were firstlydeveloped. Procedure of sample pre-treatment and condition of instruments wasoptimized.2. Based on the values of EC50and LC50, the qualitative model of risk analysisof antifouling biocides, the environmental risk model for graded the relative toxicityof marine antifouling coatings has been proposed.