A combined experimental and density functional theory study of metformin oxy-cracking for pharmaceutical wastewater treatment.

Pharmaceutical compounds are emerging contaminants that have been detected in surface water across the world. Because conventional wastewater treatment plants are not designed to treat such pollutants, new technologies are needed to degrade and oxidize such contaminants. The newly developed oxy-cracking process was utilized to treat the antidiabetic drug, metformin. The process, which involved partial oxidation of metformin in alkaline aqueous medium, proved to decompose the drug into small organic molecules, with minimum emission of CO, therefore, increasing its biodegradability and removal from industrial treatment plants. The reaction gaseous products were probed by online gas chromatography. The liquid phase before and after oxy-cracking was analyzed for total carbon content by TOC and gas chromatography mass spectrometry. The products formed from the nitrogen-rich drug included ammonia, amines, amidines, and urea derivatives. A reaction mechanism for the oxy-cracking process is proposed. Because the hydroxyl radical (˙OH) is believed to play a central role in the oxy-cracking process, the mechanism is initiated by ˙OH attacks on metformin, followed by single decomposition or isomerization steps into stable products. The reactions were investigated using density functional theory calculations and validated using high quality 2 order Møller-Plesset perturbation theory energy calculations.