CO₂, HCO₃^–, and CO₃^2– are present in all aqueous media at pH > 4 if no major effort is made to remove them. Usually the presence of CO₂/HCO₃^–/CO₃^2– is either forgotten or considered only as a buffer or proton transfer catalyst. Results obtained in the last decades point out that carbonates are key participants in a variety of oxidation processes. This was first attributed to the formation of carbonate anion radicals via the reaction OH^• + CO₃^2– → CO₃^•– + OH^–. However, recent studies point out that the involvement of carbonates in oxidation processes is more fundamental. Thus, the presence of HCO₃^–/CO₃^2– changes the mechanisms of Fenton and Fenton-like reactions to yield CO₃^•– directly even at very low HCO₃^–/CO₃^2– concentrations. CO₃^•– is a considerably weaker oxidizing agent than the hydroxyl radical and therefore a considerably more selective oxidizing agent. This requires reconsideration of the sources of oxidative stress in biological systems and might explain the selective damage induced during oxidative stress. The lower oxidation potential of CO₃^•– probably also explains why not all pollutants are eliminated in many advanced oxidation technologies and requires rethinking of the optimal choice of the technologies applied. The role of percarbonate in Fenton-like processes and in advanced oxidation processes is discussed and has to be re-evaluated. Carbonate as a ligand stabilizes transition metal complexes in uncommon high oxidation states. These high-valent complexes are intermediates in electrochemical water oxidation processes that are of importance in the development of new water splitting technologies. HCO₃^– and CO₃^2– are also very good hole scavengers in photochemical processes of semiconductors and may thus become key participants in the development of new processes for solar energy conversion. In this Account, an attempt to correlate these observations with the properties of carbonates is made. Clearly, further studies are essential to fully uncover the potential of HCO₃^–/CO₃^2– in desired oxidation processes.

Many advanced oxidation processes (AOPs) use Fenton-like reactions to degrade organic pollutants by activating peroxymonosulfate (HSO₅^-, PMS) or peroxydisulfate (S₂O₈^2-, PDS) with Fe(H₂O)₆²⁺ (Fe_aq^II). This paper presents results on the kinetics and mechanisms of reactions between Fe_aq^II and PMS or PDS in the absence and presence of bicarbonate (HCO₃^-) at different pH. In the absence of HCO₃^-, Fe_aq^IV, rather than the commonly assumed SO₄^•-, is the dominant oxidizing species. Multianalytical methods verified the selective conversion of dimethyl sulfoxide (DMSO) and phenyl methyl sulfoxide (PMSO) to dimethyl sulfone (DMSO₂) and phenyl methyl sulfone (PMSO₂), respectively, confirming the generation of Fe_aq^IV by the Fe_aq^II-PMS/PDS systems without HCO₃^-. Significantly, in the presence of environmentally relevant concentrations of HCO₃^-, a carbonate radical anion (CO₃^•-) becomes the dominant reactive species as confirmed by the electron paramagnetic resonance (EPR) analysis. The new findings suggest that the mechanisms of the persulfate-based Fenton-like reactions in natural environments might differ remarkably from those obtained in ideal conditions. Using sulfonamide antibiotics (sulfamethoxazole (SMX) and sulfadimethoxine (SDM)) as model contaminants, our study further demonstrated the different reactivities of Fe_aq^IV and CO₃^•- in the Fe_aq^II-PMS/PDS systems. The results shed significant light on advancing the persulfate-based AOPs to oxidize pollutants in natural water.