稳定同位素13C标记的sp2碳纳米材料在藻-大型蚤-稀有鮈鲫水生食物链中的传递和代谢转化研究

Carbon nanomaterials, due to their unique physical and chemical properties, have been widely applied in many consumer products. Carbon nanomaterials have become one kind of the most used commercialized nanomaterials in world. Subsequently, release of substantial amount of nanomaterials into the environment is inevitable. Understanding the safety, environmental and human health impacts of nanotechnology-based products is of worldwide importance. Therefore, researches on the biological effects of carbon nanomaterials and nanosafety in environment are urgently significant issues during the healthy and sustained development of carbon nanomaterials in our country and around world. However, little information about the environmental biological behaviors of carbon nanomaterials, so far, is available for the transportation, transformation and metabolism of carbon nanomaterials and their quantification methods in aquatic food chain and environmental systems. Sensitive, intrinsic and quantitative detection of carbon nanomaterials in environment is a key technique for studying their nanosafety and environmental risk. In this proposal, we choose the stable isotope 13C labeled graphene, SWCNTs and fullerene as the model carbon nanomaterials (flaky, tubular and spherical), detect quantitatively the change of isotope ratio 13C/12C by isotope radio mass spectrometry and combine the modern analytical technique - to investigate the transportation, transformation and metabolism of carbon nanomaterials in an Algae-Daphnia magna-Gobiocypris rarus aquatic food chain and their mechanism and regularities of interactions. We will reveal the relationships between environmental biological effects and physiochemical properties of pristine carbon nanomaterials. The proposed project will provide insights into the environmental behaviors and nanosafety of carbon nanomaterials, improve accurate and relevant data/model for the risk assessment and safe applications of carbon nanomaterials in environment.

碳纳米材料因其独特的物化性质，是纳米产品中使用最多的纳米材料之一，这些纳米材料不可避免地通过各种途径进入环境，其环境纳米安全性研究是碳纳米科技健康发展亟待解决的关键科学问题。目前，碳纳米材料在生态系统不同营养层次生物间的传递和代谢规律，因缺乏合适的定量研究方法，而未有系统、全面的数据。建立针对环境生物体系中碳纳米材料高灵敏、本征的定量检测方法，获得与环境食物链相关的数据，是推动其环境纳米生物效应和风险研究的关键。本项目选择稳定同位素13C标记的sp2碳纳米材料（片状石墨烯、管状SWCNTs和球形C60），以同位素比值-质谱仪定量检测13C/12C的比值变化，结合现代分析测试技术，研究它们在环境水生食物链（藻-大型蚤-稀有鮈鲫）的传递规律和代谢转化机制，揭示不同结构和形状、未修饰的碳纳米材料在生态系统中不同层次生物中的环境行为及其"构-效"关系，为其环境风险评估和安全使用提供重要数据和支持。

碳纳米材料在生态系统不同营养层次生物间的传递和代谢规律，因缺乏合适的定量研究方法，而未有系统、全面的数据。建立针对环境生物体系中碳纳米材料高灵敏、本征的定量检测方法，获得与环境食物链相关的数据，是推动其环境纳米生物效应和风险研究的关键。本项目选择稳定同位素13C骨架标记的富勒烯碳纳米材料，以同位素比值-质谱仪定量检测13C/12C的比值变化，结合现代分析测试技术，研究它们在不同营养级别的环境水生生物及其水生生物食物链（藻-大型蚤-斑马鱼）的累积和传递。重要结果：一：我们获得了一系列纯度较高的、标记量高达10%的稳定同位素骨架标记碳纳米材料如（富勒烯、羟基化富勒烯、羧基化富勒烯和石墨烯以及氧化石墨烯）；二：搭建了斜生栅藻-大型蚤-斑马鱼的水生生态系统的研究平台，并建立碳纳米材料的水生生物体内的定量分析方法；三：研究了碳纳米材料在大型蚤和鱼等水生环境不同营养级别生物体中的累积和代谢情况，证实了碳纳米材料在藻-大型蚤-鱼环境水生生态食物链的累积和可能的传递，评估了其在环境水生生物不同营养级别的传递效率和可能的营养级放大的风险。这些研究结果不仅为环境生物复杂体系中纳米材料的定量研究提供了可靠、灵敏的定量方法和技术；而且揭示了碳纳米材料对环境水生生物的影响和可能的危害途径，为碳纳米材料在复杂体系的生物化学机制研究和环境安全性评估，提供基础的研究数据。研究成果正式发表SCI论文6篇，连续发表在环境领域TOP期刊：Environmental Science & Technology, (2018, 52 (21), 12133-12141；2017, 51: 10146–10153；2016, 50 (19), 10421-10427). (3篇, IF=6.653)；Environmental Science-Nano, 2016, 3: 799-805. (IF=6.087)；Particle and Fibre Toxicology, 2016, 13: 1-14. (IF=6.105)；RSC Advances 2015, 5 (94), 76949-76956. (IF=2.936)；中文核心期刊2篇：中国科学：化学, 2016, 46: 173-187；生态毒理学报 2017,(05),12-25. EI收录1篇：科学通报, 2017, 62: 1714-1720。