海水养殖用塑料中有机磷酸酯的溶出规律及生物富集特征
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海南省自然科学基金面上项目(323MS011)、广东省环境污染控制与修复技术重点实验室开放基金(2023B1212060016)、海南大学生态文明协同创新项目(XTCX2022STC20)、海南大学高层次人才启动基金(XJ2300002965)、海南省科技人才创新项目(KJRC2023C11)和海南省重点项目计划(ZDYF2022SHFZ317)共同资助


Release behavior and bioaccumulation characteristics of organophosphate esters from plastics in marine aquaculture
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    摘要:

    养殖用塑料的长期使用不可避免地造成塑料添加剂溶出到水环境中。然而,这些塑料添加剂的溶出规律及对水生生物的暴露风险尚不清晰。本研究聚焦典型塑料添加剂有机磷酸酯(OPEs),以在野外海水养殖塘中收集的塑料防渗膜为研究对象,分别进行室内模拟溶出实验和水生生物暴露实验。结果显示,在240 h的模拟溶出实验中,总OPEs的溶出量为12.24 ng/g。其中,含氯类OPEs的溶出率相对较高,磷酸三(2-氯乙基)酯(TCEP)溶出率达到了40.6%,含氯类OPEs、芳香类OPEs、烷烃类OPEs溶出率依次降低;塑料防渗膜在0~2 d的溶出实验过程中,OPEs的溶出速率最快,在第6天后,溶出速率开始达到平衡状态。水生生物暴露实验结果显示,48 h内防渗膜溶出的OPEs在卤虫(Artemia)体内检出5种,其中,磷酸三甲苯基酯(TCP)、磷酸三(1,3-二氯异丙基)酯(TDCPP)的log10BAF (生物富集因子)均大于3.7,具有生物富集效应;磷酸三正丁酯(TnBP)的log10BAF值介于3.3~3.7之间,具有潜在的生物富集效应。上述结果表明,海水养殖塘中的塑料防渗膜所释放的OPEs会对水生生物造成潜在的风险。

    Abstract:

    Recently, the rapid development of the Chinese coastal economy and the expansion of aquaculture have led to an increased reliance on plastic materials within marine aquaculture systems. These materials, such as impermeable membranes, fishing nets, buoys, cages, and ropes, are extensively used for their beneficial properties. They are lightweight, durable, and cost-effective. However, the large-scale production and extensive use of plastics in aquaculture have increased concerns about their potential environmental impacts, particularly regarding the pollution of the marine environment and the associated risks to ecosystems. The primary concern is the plastic additives that are incorporated into these materials. These additives, including organophosphate esters (OPEs), are often physically mixed into the polymer matrices rather than chemically bonded. This physical integration increases their susceptibility to release into the surrounding environment through various processes, such as volatilization, leaching, abrasion, and dissolution, during the product’s lifecycle. Despite these risks, the mechanisms and patterns of additive release, as well as the exposure risks presented to marine organisms, remain poorly understood. This study focused explicitly on OPEs, a common group of plastic additives, to investigate their presence and behavior in plastic impermeable membranes used in marine aquaculture ponds. The study aimed to (1) identify the types and concentrations of OPEs present in the plastic impermeable membranes collected from marine aquaculture ponds, (2) simulate the dynamic dissolution of these OPEs in artificial seawater, and (3) evaluate the bioaccumulation potential of these OPEs in aquatic organisms, using Artemia as a model species. We collected plastic impermeable membranes from wild marine aquaculture ponds and analyzed their OPE content using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Our analysis revealed the presence of seven different types of OPEs, which included three aliphatic OPEs (TnBP and TiBP), one aromatic OPE (TCP), and three chlorinated OPEs (TCEP, TDCPP, and TCPP). TCPP was the most abundant, with a concentration of (395.15±48.05) ng/g, accounting for 63.12% of the total OPEs detected in the membranes. TnBP followed, exhibiting concentration of (52.96±5.25) ng/g. In contrast, TCP had the lowest concentration, contributing only 0.33% to the total OPEs. To understand the dissolution behavior of OPEs in these membranes, we conducted a 240-h laboratory simulation. The impermeable membranes were submerged in artificial seawater with a salinity of 30, and water samples were collected every 48 h for analysis. The OPE concentrations in these water samples were determined using solid-phase extraction (SPE) followed by HPLC-MS/MS. At the end of the experiment, the total amount of OPEs dissolved from the membranes reached 12.24 ng/g. Chlorinated OPEs exhibited the highest dissolution rates, with TCEP showing a dissolution rate of 40.6%. The general dissolution order was chlorinated OPEs > aromatic OPEs > aliphatic OPEs. Notably, the dissolution rate was highest during the first 48 h of the experiment and then gradually decreased over time. By approximately day 6, the dissolution rate reached a near-equilibrium state, likely due to the depletion of OPEs from cracks and pores on the membrane surface. At this stage, the membranes had likely reached a dynamic equilibrium between the release and adsorption of OPEs. In addition to the dissolution experiments, we assessed the bioaccumulation potential of OPEs in Artemia, a species commonly used in marine studies. Plastic impermeable membranes were added to artificial seawater at concentrations that mimicked those typically found in marine aquaculture ponds. After exposure, Artemia and the surrounding water samples were collected, and the OPE concentrations were analyzed using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Five OPEs—TCP, TDCPP, TnBP, TCPP, and TiBP—were detected in Artemia. We evaluated the degree of bioaccumulation using the bioaccumulation factor (BAF). The results indicated that TCP and TDCPP had significant bioaccumulation potential, with logBAF values greater than 3.7. TnBP exhibited a moderate bioaccumulation effect, with a logBAF between 3.3 and 3.7. However, TCPP and TiBP showed no significant bioaccumulation potential, as their logBAF values were below 3.3. In conclusion, our study identified six distinct OPEs in the plastic impermeable membranes used in marine aquaculture, with chlorinated OPEs being the most prevalent. The results of the dissolution experiments revealed that OPEs are initially released rapidly from surface cracks and pores of the membranes, followed by a slower release as equilibrium is reached. Furthermore, the bioaccumulation experiments demonstrated that certain OPEs, particularly TCP and TDCPP, present bioaccumulation risks to marine organisms such as Artemia. These findings underscore the importance of managing plastic additives in marine aquaculture systems to mitigate the potential environmental impacts of plastic waste and its associated contaminants. The study provides valuable insights that can inform future strategies for reducing the ecological risks of plastic additives in marine environments.

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杨芷,刘冬妮,黄圣南,戴雪田,钱伟,朱小山.海水养殖用塑料中有机磷酸酯的溶出规律及生物富集特征.渔业科学进展,2025,46(4):78-88

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  • 收稿日期:2024-10-11
  • 最后修改日期:2024-12-03
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  • 在线发布日期: 2025-07-14
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