Reactive species in advanced oxidation processes: Formation, identification and reaction mechanism

Chemical oxidants have been applied in water treatment for more than a century, first as disinfectants and later to abate inorganic and organic contaminants. The challenge of oxidative abatement of organic micropollutants is the formation of transformation products with unknown (eco)toxicological consequences. Four aspects need to be considered for oxidative micropollutant abatement: (i) Reaction kinetics, controlling the efficiency of the process, (ii) mechanisms of transformation product formation, (iii) extent of formation of disinfection byproducts from the matrix, (iv) oxidation induced biological effects, resulting from transformation products and/or disinfection byproducts. It is impossible to test all the thousands of organic micropollutants in the urban water cycle experimentally to assess potential adverse outcomes of an oxidation. Rather, we need multidisciplinary and automated knowledge-based systems, which couple predictions of kinetics, transformation and disinfection byproducts and their to...

Oxidation Processes in Water Treatment: Are We on Track?

Effect of inorganic anions on the performance of advanced oxidation processes for degradation of organic contaminants

The presence of organic contaminants in wastewater poses considerable risks to the health of both humans and ecosystems. Although advanced oxidation processes that rely on highly reactive radicals to destroy organic contaminants are appealing treatment options, substantial energy and chemical inputs limit their practical applications. Here we demonstrate that Cu single atoms incorporated in graphitic carbon nitride can catalytically activate H2O2 to generate hydroxyl radicals at pH 7.0 without energy input, and show robust stability within a filtration device. We further design an electrolysis reactor for the on-site generation of H2O2 from air, water and renewable energy. Coupling the single-atom catalytic filter and the H2O2 electrolytic generator in tandem delivers a wastewater treatment system. These findings provide a promising path toward reducing the energy and chemical demands of advanced oxidation processes, as well as enabling their implementation in remote areas and isolated communities.

Organic wastewater treatment by a single-atom catalyst and electrolytically produced H2O2.

Comparison of the UV/chlorine and UV/H2O2 processes in the degradation of PPCPs in simulated drinking water and wastewater: Kinetics, radical mechanism and energy requirements.

Utilities incorporating the potable reuse of municipal wastewater are interested in converting from the UV/H2O2 to the UV/free chlorine advanced oxidation process (AOP). The AOP treatment of reverse osmosis (RO) permeate often includes the de facto UV/chloramine AOP because chloramines applied upstream permeate RO membranes. Models are needed that accurately predict oxidant photolysis and subsequent radical reactions. By combining radical scavengers and kinetic modeling, we have derived quantum yields for radical generation by the UV photolysis of HOCl, OCl-, and NH2Cl of 0.62, 0.55, and 0.20, respectively, far below previous estimates that incorporated subsequent free chlorine or chloramine scavenging by the •Cl and •OH daughter radicals. The observed quantum yield for free chlorine loss actually decreased with increasing free chlorine concentration, suggesting scavenging of radicals participating in free chlorine chain decomposition and even free chlorine reformation. Consideration of reactions of •ClO and its daughter products (e.g., ClO2-), not included in previous models, were critical for modeling free chlorine loss. Radical reactions (indirect photolysis) accounted for ∼50% of chloramine decay and ∼80% of free chlorine loss or reformation. The performance of the UV/chloramine AOP was comparable to the UV/H2O2 AOP for degradation of 1,4-dioxane, benzoate and carbamazepine across pH 5.5-8.3. The UV/free chlorine AOP was more efficient at pH 5.5, but only by 30% for 1,4-dioxane. At pH 7.0-8.3, the UV/free chlorine AOP was less efficient. •Cl converts to •OH. The modeled •Cl:•OH ratio was ∼20% for the UV/free chlorine AOP and ∼35% for the UV/chloramine AOP such that •OH was generally more important for contaminant degradation.

Comparing the UV/Monochloramine and UV/Free Chlorine Advanced Oxidation Processes (AOPs) to the UV/Hydrogen Peroxide AOP Under Scenarios Relevant to Potable Reuse.

Curtis J. Chinn

Papers

Comparing the UV/Monochloramine and UV/Free Chlorine Advanced Oxidation Processes (AOPs) to the UV/Hydrogen Peroxide AOP Under Scenarios Relevant to Potable Reuse.