Coupling Experimental and Theoretical Molecular-Level Investigations to Visualize the Fate of Degradation of Organic Compounds in Aqueous Phase Advanced Oxidation Systems

1435926米纳卡耦合实验和理论分子水平研究可视化水相高级氧化系统中有机化合物降解的命运缺乏总体管理计划，加上微量已知和新出现的有机化合物对人体健康和生态影响的不确定性，引起了公众对水的关注。这些问题也对处理实际和计划中的废水回用的下一代水处理公用事业公司提出了重大挑战。产生高活性羟基自由基的高级氧化过程是控制微量有机化合物的有前途的技术。虽然羟基自由基诱导的与多种有机化合物反应的初始命运已经被研究过，但产生中间自由基和稳定副产物的机制还不清楚。我们对复杂的多通道基本反应途径的理解仍然存在重大障碍，这些反应途径嵌入过氧自由基双分子衰变中，产生相同的中间自由基和稳定的副产物。在这项研究过程中开发的模型将使研究人员和政策制定者能够预测可能的化学副产品和替代方案，从而对直接饮用这种水的普通公众或间接接触这种水的其他生态生物造成最小的不利影响。拟议的研究将整合三个推力，以发现目前未知的三种主要降解途径的命运。首先，我们将进行脉冲光解动力学测量，以确定多通道过氧自由基反应的温度依赖性总反应速率常数。我们还将使用质谱法测量产生的副产品。其次，我们将采用量子力学理论计算来确定基本反应途径和相关的反应速率常数。第三，我们将把我们的动力学测量和我们的理论计算结合起来，开发一个基于主体的模型，使我们能够可视化和预测有机化合物的命运。通过在模拟反应网络中嵌入明确指定的反应规则和分子行为，由此产生的基于代理的模型将使用软件代理来表示自由基和有机化合物，然后模拟它们的相互作用，以预测随时间和空间变化的相应后果（即副产品）。最后，实验观察将验证基于主体的模型的结果。

1435926MinakataCoupling Experimental and Theoretical Molecular-Level Investigations to Visualize the Fate of Degradation of Organic Compounds in Aqueous Phase Advanced Oxidation SystemsThe lack of an overarching management plan combined with uncertainty about the adverse human health and ecological impacts of trace amounts of known and emerging organic compounds have raised public concerns about water. These issues also present major challenges to next generation water treatment utilities dealing with de facto and planned wastewater reuse. Advanced oxidation processes that produce highly reactive hydroxyl radicals are promising technologies to control trace amounts of organic compounds. Although the initial fate of hydroxyl radical induced reactions with diverse organic compounds have been studied, the mechanisms that produce intermediate radicals and stable-byproducts are not well understood. Significant barriers remain in our understanding of complex multi-channel elementary reaction pathways embedded in peroxyl radical bimolecular decay that produce identical intermediate-radicals and stable-byproducts. The model developed in the course of this research will give researchers and policy makers the ability to predict the likely chemical by-products and alternative options to provide least adverse impact on the general public who will directly consume this water or other ecological organisms who will be exposed indirectly.The proposed study will integrate three thrusts to discover the currently unknown fate of the three major degradation pathways. First, we will perform pulse-photolysis kinetic measurement to determine the temperature-dependent overall reaction rate constants for multi-channel peroxyl radical reactions. We will also measure the resulting byproducts using a mass spectrometry. Second, we will employ quantum mechanical theoretical calculations to determine the elementary reaction pathways and associated reaction rate constants. Third, we will then combine our kinetic measurements with our theoretical calculations to develop an agent-based model that will enable us to visualize and predict the fate of organic compounds. With explicitly assigned reaction rules and molecular behavior embedded within a simulated reaction network, the resulting agent-based model will use software agents to represent radical species and organic compounds and then simulate their interactions to predict corresponding consequences (i.e., byproducts) over time and space. Finally, experimental observations will validate the outcomes from the agent-based model.