The monitoring of Advanced Oxidation/Reduction Processes (AO/RPs) for the evaluation of the yield and mechanisms of decomposition of perfluorinated compounds (PFCs) is often a more difficult task than their determination in the environmental, biological or food samples with complex matrices. This is mostly due to the formation of hundreds, or even thousands, of both intermediate and final products. The considered AO/RPs, involving free radical reactions, include photolytic and photocatalytic processes, Fenton reactions, sonolysis, ozonation, application of ionizing radiation and several wet oxidation processes. The main attention is paid to the most commonly occurring PFCs in the environment, namely PFOA and PFOS. The most powerful and widely exploited method for this purpose is without a doubt LC/MS/MS, which allows the identification and trace quantitation of all species with detectability and resolution power depending on the particular instrumental configurations. The GC/MS is often employed for the monitoring of volatile fluorocarbons, confirming the formation of radicals in the processes of C‒C and C‒S bonds cleavage. For the direct monitoring of radicals participating in the reactions of PFCs decomposition, the molecular spectrophotometry is employed, especially electron paramagnetic resonance (EPR). The UV/Vis spectrophotometry as a detection method is of special importance in the evaluation of kinetics of radical reactions with the use of pulse radiolysis methods. The most commonly employed for the determination of the yield of mineralization of PFCs is ion-chromatography, but there is also potentiometry with ion-selective electrode and the measurements of general parameters such as Total Organic Carbon and Total Organic Fluoride. The presented review is based on about 100 original papers published in both analytical and environmental journals.

监测高级氧化/还原过程（AO / RPs）以评估全氟化合物（PFCs）的产率和分解机理通常比在具有复杂基质的环境，生物或食品样品中测定更为困难。这主要是由于形成了数百甚至数千个中间产品和最终产品。所考虑的AO / RPs涉及自由基反应，包括光解和光催化过程，Fenton反应，声解，臭氧化，电离辐射的应用以及几种湿式氧化过程。主要关注环境中最常见的PFC，即PFOA和PFOS。毫无疑问，用于此目的的最强大，最广泛使用的方法是LC / MS / MS，从而可以根据特定的仪器配置对所有物种进行识别和痕量定量，并具有可检测性和分辨力。GC / MS通常用于监测挥发性碳氟化合物，从而确认C‒C和C‒S键断裂过程中自由基的形成。为了直接监控参与PFC分解反应的自由基，使用了分子分光光度法，尤其是电子顺磁共振（EPR）。UV / Vis分光光度法作为检测方法，在使用脉冲辐射分解方法评估自由基反应动力学时特别重要。确定PFC矿化产率的最常用方法是离子色谱法，但是也有带离子选择电极的电位计和一般参数的测量，例如总有机碳和总有机氟化物。提出的评论是基于在分析和环境期刊上发表的大约100篇原始论文。