Urine, which is an important waste biomass resource, is the main source of nitrogen in sewage and contains large quantities of emerging contaminants (ECs). In this study, we propose a new method to efficiently remove urine, simultaneously eliminate ECs, and control the generation of toxic chlorate during urine treatment using a photoelectrocatalytic-chlorine (PEC-Cl) system. A type-II heterojunction of WO₃/BiVO₄ was used as a photoanode to generate chlorine radicals (Cl•) by decreasing the oxidation potential of WO₃ valence band for the highly selective conversion of urine to N₂ and the simultaneous degradation of ECs in an efficient manner. The method presented surprising results. It was observed that the amount of toxic chlorate was significantly inhibited by circumventing the over-oxidation of Cl⁻ by holes or hydroxyl radicals (•OH). Moreover, the removal of urea nitrogen reached 97% within 90 min, while the degradation rate of trimethoprim in urine was above 98.6% within 60 min, which was eight times more than that in the PEC system (12.1%). Compared to the bare WO₃ photoanode, the toxic chlorate and nitrate generated by the WO₃/BiVO₄ heterojunction photoanode decreased by 61% and 44%, respectively. Thus, this study provides a safe, efficient, and environmentally-friendly approach for the disposal of urine.

In agricultural lowland landscapes, intensive agricultural is accompanied by a wide use of agrochemical application, like pesticides and fertilizers. The latter often causes serious environmental threats such as N compounds leaching and surface water eutrophication; additionally, since perchlorate can be present as impurities in many fertilizers, the potential presence of perchlorates and their by-products like chlorates and chlorites in shallow groundwater could be a reason of concern. In this light, the present manuscript reports the first temporal and spatial variation of chlorates, chlorites and major anions concentrations in the shallow unconfined aquifer belonging to Ferrara province (in the Po River plain). The study was made in 56 different locations to obtain insight on groundwater chemical composition and its sediment matrix interactions.During the monitoring period from 2010 to 2011, in June 2011 a nonpoint pollution of chlorates was found in the shallow unconfined aquifer belonging to Ferrara province. Detected chlorates concentrations ranged between 0.01 and 38 mg/l with an average value of 2.9 mg/l. Chlorates were found in 49 wells out of 56 and in all types of lithology constituting the shallow aquifer. Chlorates concentrations appeared to be linked to NO3−, volatile fatty acids (VFA) and oxygen reduction potential (ORP) variations. Chlorates behaviour was related to the biodegradation of perchlorates, since perchlorates are favourable electron acceptors for the oxidation of labile dissolved organic carbon (DOC) in groundwater. Further studies must take into consideration to monitor ClO4− in pore waters and groundwater to better elucidate the mass flux of ClO4− in shallow aquifers belonging to agricultural landscapes.

Roxarsone (ROX), an organoarsenic feed additive, can be discharged into aquatic environment and photodegraded into more toxic inorganic arsenics. However, the photodegradation behavior of ROX in aquatic environment is still unclear. To better understand ROX photodegradation behavior, the influencing factors, photodegradation mechanism, and process modelling of ROX photodegradation were investigated in this study. The results showed that ROX in the aquatic environment was degraded to inorganic As(III) and As(V) under light irradiation. The degradation efficiency was enhanced by 25% with the increase of light intensity from 300 to 800 μW/cm² via indirect photolysis. The photodegradation was temperature dependence, but was only slightly affected by pH. Nitrate ion (NO₃⁻) had an obvious influence, but sulfate, carbonate, and chlorate ions had a negligible effect on ROX degradation. Dissolved organic matter (DOM) in the solution inhibited the photodegradation. ROX photodegradation was mainly mediated by reactive oxygen species (in the form of single oxygen ¹O₂) generated through ROX self-sensitization under irradiation. Based on the data of factors affecting ROX photodegradation, ROX photodegradation model was built and trained by an artificial neural network (ANN), and the predicted degradation rate was in good agreement with the real values with a root mean square error of 1.008. This study improved the understanding of ROX photodegradation behavior and provided a basis for controlling the pollution from ROX photodegradation.

Sulfate radical (•SO₄⁻)–based advanced oxidation processes have attracted a great deal of attention for use in water disinfection because of their strong oxidation ability toward electron-rich moieties on microorganism molecules. However, a few studies have focused on the effects of •SO₄⁻ on pathogenic microorganism inactivation in marine aquaculture water containing various inorganic anions. We employed the gram-negative bacteria E. coli and gram-positive bacteria S. agalactiae as representatives to evaluate the application of UV/persulfate (S₂O₈²⁻, PDS), to the disinfection of marine aquaculture water in a comprehensive manner. Total inactivation of 4.13ˍlog of E. coli cells and 4.74ˍlog of S. agalactiae cells was reached within 120 s in the UV/PDS system. The inactivation of pathogenic bacteria in marine aquaculture water increased with the increasing PDS concentration and UV intensity. An acidic pH was beneficial for UV/PDS inactivation. Halogen-free radicals showed a strong influence on the inactivation. Anions in seawater, including Cl⁻, Br⁻, and HCO₃⁻ inhibited the disinfection. The inactivation rates of pathogenic bacteria followed the order seawater < marine aquaculture water < freshwater. Pathogenic bacteria could also be effectively inactivated in actual marine aquaculture water and reservoir water. The analysis of the inactivation mechanisms showed that S₂O₈²⁻ was activated by UV to produce •SO₄⁻, which damaged the cell membranes. In addition, antioxidant enzymes, including SOD and CAT, were induced. The genomic DNA was also damaged. Inorganic disinfection byproducts such as chlorate and bromate were not formed during the disinfection of marine aquaculture water, which indicated that UV/PDS was a safe and efficient disinfection method.

The experimental investigation of chloride ion oxidation under the action of ozone and ultraviolet radiation with wavelength 254 nm in the bulk of acid aqueous solution at pH 0–2 has been performed. Processes of chloride oxidation in these conditions are the same as the chemical reactions in the system O₃ – OH – Cl⁻(aq). Despite its importance in the environment and for ozone-based water treatment, this reaction system has not been previously investigated in the bulk solution. The end products are chlorate ion ClO₃ ⁻ and molecular chlorine Cl₂. The ions of trivalent iron have been shown to be catalysts of Cl⁻ oxidation. The dependencies of the products formation rates on the concentrations of O₃ and H⁺ have been studied. The chemical mechanism of Cl⁻ oxidation and Cl₂ emission and ClO₃ ⁻ formation has been proposed. According to the mechanism, the dominant primary process of chloride oxidation represents the complex interaction with hydroxyl radical OH with the formation of Cl₂ ⁻ anion-radical intermediate. OH radical is generated on ozone photolysis in aqueous solution. The key subsequent processes are the reactions Cl₂ ⁻ + O₃ → ClO + O₂ + Cl⁻ and ClO + H₂O₂ → HOCl + HO₂. Until the present time, they have not been taken into consideration on mechanistic description and modelling of Cl⁻ oxidation. The final products are formed via the reactions 2ClO → Cl₂O₂, Cl₂O₂ + H₂O → 2H⁺ + Cl⁻ + ClO₃ ⁻ and HOCl + H⁺ + Cl⁻ ⇄ H₂O + Cl₂. Some portion of chloride is oxidized directly by O₃ molecule with the formation of molecular chlorine in the end.