Transformation of hydroxylamine to nitrosated and nitrated products during advanced oxidation process.

Recently, hydroxylamine (HAm) was introduced to drive advanced oxidation processes (AOPs) for removing organic contaminants. However, we found that HAm-driven Cu(II)/peroxymonosulfate oxidation of phenol produced p-nitrosophenol, 2-nitrophenol and 4-nitrophenol. The total nitro(so) products accounted for approximately 25.0 % of the phenol transformation at certain condition. SO4•- and •OH were identified as the primary and second significant oxidants, respectively. Reactive nitrogen species (RNS) were involved in phenol transformation. The pathway and mechanism of HAm transformation in HAm-driven transition metal ion-catalyzed AOPs were proposed for the first time in this study. The product of HAm via twice single-electron oxidation by Cu(II) is nitroxyl (HNO/NO-), which is a critical oxidation intermediate of HAm. Further oxidation of HNO by SO4•- or •OH is the initial step in propagating radical chain reactions, leading to nitric oxide radical (•NO) and nitrogen dioxide radical (•NO2) as the primary RNS. HAm is a critical intermediate in natural nitrogen cycle, suggesting that HAm can drive the oxidation processes of pollutants in natural environments. Nitro(so) products will be readily produced when AOPs are applied for ecological remediation. This study highlights the formation of toxic nitrosated and nitrated products in HAm-driven AOPs, and the requirement of risk assessments to evaluate the possible health and ecological impacts.

A novel diagnostic method for distinguishing between Fe(IV) and •OH by using atrazine as a probe: Clarifying the nature of reactive intermediates formed by nitrilotriacetic acid assisted Fenton-like reaction.

In this work, we found that the distribution of two specific atrazine (ATZ) oxidation products (desethyl-atrazine (DEA) and desisopropyl-atrazine (DIA)) was different in oxidation processes involving aqueous ferryl ion (Fe(IV)) species and •OH. Specifically, the molar ratio of produced DEA to DIA (i.e., [DEA]/[DIA]) increased from 7.5 to 13 with increasing pH from 3 to 6 when ATZ was oxidized by Fe(IV), while the treatment of ATZ by •OH led to the [DEA]/[DIA] value of 2 which was independent of pH. Moreover, ATZ showed high reactivity towards Fe(IV) over a wide pH range, especially at near-neutral pH, at which ATZ oxidation in Fe(II)/peroxydisulfate system was even much faster than another well-defined Fe(IV) scavenger, the sulfoxides. By using this approach, it was obtained that the [DEA]/[DIA] value remained at 2 during ATZ transformation by the nitrilotriacetic acid (NTA) assisted Fenton-like (Fe(III)/H2O2) system, which was independent of solution pH and reactants dosage. This result clarified that •OH was the primary reactive intermediate formed in the NTA assisted Fe(III)/H2O2 system. This study not only developed a novel sensitive diagnostic tool for distinguishing Fe(IV) from •OH, but also provided more credible evidence to the nature of reactive intermediate in a commonly controversial system.