船舶压载水羟基自由基处理及其相关化学物质监测研究
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摘要
外来生物入侵性传播已经被全球环境基金组织(GEF)确认为危害海洋的四大污染源之一,船舶压载水异地排放是引起外来生物入侵性传播的主要途径。本文针对防治海洋外来生物入侵性传播和保护近岸海域生态安全的国际重大需求,依托“十一五”国家科技支撑计划重点项目“远洋船舶压载水羟基自由基工程化处理技术开发”(No.2006BAC11B06)和国际科技合作重点项目“羟基自由基杀灭船舶压载水外来入侵生物的研究”(No.2005DFA20800),应用大气压强电场电离放电方法,通过天然物质H20和O2为原料制备·OH等氧活性粒子溶液,对船舶压载水的·OH治理进行了研究,主要内容如下：
介绍了实现强电场放电的原理和方法,阐明了02、H20在强电场放电形式下生成·OH的等离子体化学反应机理;通过积分法研究了·OH处理后压载水中TRO浓度衰减的反应动力学规律,得到了TRO衰减速率常数,确定海水中TRO衰减近似为一级反应,推导出预测处理后压载水中TRO浓度变化的速率公式；以邻羟基苯甲酸(SA)为·OH捕捉剂,通过HPLC测定SA羟基化产物含量确定生成-OH浓度,建立了海水中·OH的定量检测方法；通过带有电导检测器的离子色谱仪,建立了处理后压载水中一种相关化学物质Br03-的检测方法。
依据国际海事组织(IMO)《压载水管理系统认指南(G8)》认可的实验标准,完成了基于《使用活性物质的压载水管理系统批准的程序G9》的船舶压载水·OH处理实验,结果表明：当致死时间为6 s时,压载水中活藻浓度<10 cell/mL、细菌未检出,处理结果达到IMO《船舶压载水及沉积物控制和管理国际公约》D-2排放标准,且24、120 h内无再生现象；处理后压载水的污染程度降低,水质得到了明显改善,减轻了压载水排放过程中对排放水域的环境压力,保证了对排放地水生生物的安全性；处理后压载水中0h、24h、120h的卤代烷烃、卤代乙酸、卤代乙腈和BrO3-等18种相关化学物质含量均低于世界卫生组织(WHO)《饮用水水质标准》。
船舶压载水·OH处理技术实现了在船上在压载水输送过程中杀灭外来有害生物。在航运业推广该项技术,可以为打破国际航运壁垒、开拓全球航运市场提供技术支撑,应用前景广,具有重大的经济效益和社会效益。
Global Environment Facility(GEF) has identified that marine invasive alien species spread is one of the four major risk factors which threates global marine environmental safety. Ballast water discharge is the main way for the spread of invasive alien species.According to the great needs of management of marine invasive alien species spread and of protection the coastal ecological safety, and depending on Key Projects in the National Science & Technology Pillar Program During the Eleventh Five-Year Plan Period(No.2006BAC11B06) and Science & Technology Cooperation Program of China (No.2005DFA20800),·OH and other reactive oxygen particles were prepared by natural substances H2O and O2 through strong electric field ionization discharge atmospheric pressure. The treatment ship's ballast water by·OH was studied in this paper. The main studies are as follows.
Principle and method of strong electric field discharge was introduced, and plasma chemical mechanism for the generation·OH from H2O and O2 through the discharge was explained. Integration method is employed to establish reaction kinetics for TRO decay in ballast water treated by·OH. The rate constant of TRO decay was obtained.And then confirming that the decay reaction in ballast water was first-order reaction approximately. The rate equation which predicts changing of TRO concentration in treated ballast water was derived. The quantitative detection method for·OH was established through measuring·OH scavenger salicylic acid (SA) by high performance liquid chromatography(HPLC). A test method for bromate, one of the relative chemicals in treated ballast water, was established using ion chromatograph equipping with electric conductance detector.
According to the land-based test standard of International Maritime Organization(IMO) Guidelines for Approval of Ballast Water Management Systems(G8) entirely, the experiment of treatment ship's ballast water by·OH based on IMO guideline Procedure for Approval of Ballast Water Management Systems That Make Use of Active Substances(G9) had finished successfully. The results show that the concentration of alage was lower than 10 cell/mL, and no bacteria were detected after being treated for 6 s. The alage and bacteria did not revival during 24 h and 120 h, respectively. It complies with Regulation D-2 of International Convention for the Control and Management of Ships'Ballast Water and Sediments completely. The pollution level of treaed ballast water decreased. And the water quality was improved, which relieves the environmental pressure when the treated ballas water was dischanged. The results show that the concents for 18 kinds of reative chemicals, such as halogenated alkanes, haloacetic acids, halogenated acetonitrile, and bromate, and so on, were all lower than World Health Organization (WHO) criterion at 0 h,24 h,120 h, also.
The technology for killing invasive alien aquatic organisms by·OH in the course of conveying ballast water in ships can provide technical support for breaking trading barriers and opening up the global shipping market and bring to great economic and social benefits.
介绍了实现强电场放电的原理和方法,阐明了02、H20在强电场放电形式下生成·OH的等离子体化学反应机理;通过积分法研究了·OH处理后压载水中TRO浓度衰减的反应动力学规律,得到了TRO衰减速率常数,确定海水中TRO衰减近似为一级反应,推导出预测处理后压载水中TRO浓度变化的速率公式；以邻羟基苯甲酸(SA)为·OH捕捉剂,通过HPLC测定SA羟基化产物含量确定生成-OH浓度,建立了海水中·OH的定量检测方法；通过带有电导检测器的离子色谱仪,建立了处理后压载水中一种相关化学物质Br03-的检测方法。
依据国际海事组织(IMO)《压载水管理系统认指南(G8)》认可的实验标准,完成了基于《使用活性物质的压载水管理系统批准的程序G9》的船舶压载水·OH处理实验,结果表明：当致死时间为6 s时,压载水中活藻浓度<10 cell/mL、细菌未检出,处理结果达到IMO《船舶压载水及沉积物控制和管理国际公约》D-2排放标准,且24、120 h内无再生现象；处理后压载水的污染程度降低,水质得到了明显改善,减轻了压载水排放过程中对排放水域的环境压力,保证了对排放地水生生物的安全性；处理后压载水中0h、24h、120h的卤代烷烃、卤代乙酸、卤代乙腈和BrO3-等18种相关化学物质含量均低于世界卫生组织(WHO)《饮用水水质标准》。
船舶压载水·OH处理技术实现了在船上在压载水输送过程中杀灭外来有害生物。在航运业推广该项技术,可以为打破国际航运壁垒、开拓全球航运市场提供技术支撑,应用前景广,具有重大的经济效益和社会效益。
Global Environment Facility(GEF) has identified that marine invasive alien species spread is one of the four major risk factors which threates global marine environmental safety. Ballast water discharge is the main way for the spread of invasive alien species.According to the great needs of management of marine invasive alien species spread and of protection the coastal ecological safety, and depending on Key Projects in the National Science & Technology Pillar Program During the Eleventh Five-Year Plan Period(No.2006BAC11B06) and Science & Technology Cooperation Program of China (No.2005DFA20800),·OH and other reactive oxygen particles were prepared by natural substances H2O and O2 through strong electric field ionization discharge atmospheric pressure. The treatment ship's ballast water by·OH was studied in this paper. The main studies are as follows.
Principle and method of strong electric field discharge was introduced, and plasma chemical mechanism for the generation·OH from H2O and O2 through the discharge was explained. Integration method is employed to establish reaction kinetics for TRO decay in ballast water treated by·OH. The rate constant of TRO decay was obtained.And then confirming that the decay reaction in ballast water was first-order reaction approximately. The rate equation which predicts changing of TRO concentration in treated ballast water was derived. The quantitative detection method for·OH was established through measuring·OH scavenger salicylic acid (SA) by high performance liquid chromatography(HPLC). A test method for bromate, one of the relative chemicals in treated ballast water, was established using ion chromatograph equipping with electric conductance detector.
According to the land-based test standard of International Maritime Organization(IMO) Guidelines for Approval of Ballast Water Management Systems(G8) entirely, the experiment of treatment ship's ballast water by·OH based on IMO guideline Procedure for Approval of Ballast Water Management Systems That Make Use of Active Substances(G9) had finished successfully. The results show that the concentration of alage was lower than 10 cell/mL, and no bacteria were detected after being treated for 6 s. The alage and bacteria did not revival during 24 h and 120 h, respectively. It complies with Regulation D-2 of International Convention for the Control and Management of Ships'Ballast Water and Sediments completely. The pollution level of treaed ballast water decreased. And the water quality was improved, which relieves the environmental pressure when the treated ballas water was dischanged. The results show that the concents for 18 kinds of reative chemicals, such as halogenated alkanes, haloacetic acids, halogenated acetonitrile, and bromate, and so on, were all lower than World Health Organization (WHO) criterion at 0 h,24 h,120 h, also.
The technology for killing invasive alien aquatic organisms by·OH in the course of conveying ballast water in ships can provide technical support for breaking trading barriers and opening up the global shipping market and bring to great economic and social benefits.
引文
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