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Featured Application: Understanding leachate treatment systems through organic matter monitoring. The presence of refractory compounds in stabilized leachates makes treatment complex. In leachate treatment systems, the lack of data on the characterization of leachates and effluents makes it difficult to track and explain the evolution of organic matter. In this study, the fractionation of chemical oxygen demand (COD) and humic substances, including humic acids (HA) and fulvic acids (FA), in addition to the application of spectroscopic techniques (Fourier transform infrared and ultraviolet–visible spectroscopy), were used to solve this data gap. A treatment system was proposed: electro-coagulation (EC) and electro-oxidation (EO). Optimal conditions (maximum COD removal) were EC, I: 4.3 A, stirring: 120 revolutions per minute, and pH: 7; EO, added NaCl: 1.0 g L−1, distance between electrodes: 0.75 cm, I: 2 A, and pH: 7. Under optimal conditions COD, HA, and FA % removals were achieved: EC: 64, 69, and 63; EO: 83, 40, and 55; respectively. In EC, the % of biodegradable COD increased from 26 to 39 and in EO it increased from 39 to 58. The biodegradability index increased from 0.094 to 0.26 with EC and reached 0.46 with EO. The generated data allowed us to establish the transformations of organic matter in the process, which was useful for understanding the processes and functioning as a tool for improving treatment systems. [ABSTRACT FROM AUTHOR]