Ran Yin

Natural magnetic pyrrhotite as a high-Efficient persulfate activator for micropollutants degradation: Radicals identification and toxicity evaluation

This study discusses the SO4- based process mediated by natural magnetic pyrrhotite (NP) for the degradation of refractory organic micropollutants. Complete degradation of 20μM phenol in distilled water (DW) was obtained within 20min using NP/PS (persulfate) system. Electron paramagnetic resonance spectra indicated aerobic and acidic conditions favored the generation of both SO4- and OH species, but only OH signal was survived at alkaline condition. The leaked Fe2+ and Fe(II) of NP collectively work to activate PS and generate surface and bulk SO4- and OH simultaneously. The identified intermediates indicate the transformation of benzene ring is the key step for phenol degradation by NP/PS system. Moreover, phenol degradation was greatly inhibited in surface water (SW, 29%) and wastewater (WW, 1%), but 25.9% and 17.5% of TOC removal were obtained in the SW and WW during NP/PS treatment, respectively. Additionally, the acute toxicity tests for NP/PS process exhibited a fluctuating trend depending on the water matrix, while the genotoxic activity analysis indicated that the treated phenol solutions were not genotoxic but cytotoxic. Overall, this study provides a solution to abate refractory organic micropollutants in water systems.

Applicability of light sources and the inner filter effect in UV/acetylacetone and UV/H2O2 processes

Light source is a crucial factor in the application of a photochemical process, which determines the energy efficiency. The performances of acetylacetone (AA) in conversion of aqueous contaminants under irradiation with a low-pressure mercury lamp, a medium-pressure mercury lamp, a xenon lamp, and natural sunlight were investigated and compared with those of H2O2 as reference. In all cases, AA was superior to H2O2 in the degradation of Acid Orange 7. Using combinations of the different light sources with various cut-off and band-pass filters, the spectra responses of the absorbed photons in the UV/AA and UV/H2O2 processes were determined for two colored and two colorless compounds. The photonic efficiency (φ) of the two photochemical processes was found to be target-dependent. A calculation approach for the inner filter effect was developed by taking the obtained φ into account, which provides a more accurate indication of the reaction mechanisms.

Effects of water chemistry on decolorization in three photochemical processes: Pro and cons of the UV/AA process

The poor selectivity of hydroxyl radicals is a major restriction in the practical application of the UV/H2O2 process for dyeing wastewater treatment. As an alternative, the target-selective UV/acetylacetone (AA) process was found highly efficient for dye decolorization. For the proper selection and application of the two photochemical processes, the effects of water matrices, including common inorganic anions (Cl-, SO42-, NO3-, HCO3-), natural organic matter, metal cations (Mg2+, Mn2+, Cu2+, Fe3+, Cr3+), and temperature, on the photo-degradation of an azo dye, Acid Orange 7 (AO7), were systematically investigated. The experimental results demonstrate that the UV/AA process was more sensitive to inner filter effect. NO3-, Cu2+, and Fe3+ were all detrimental to the UV/AA process, whereas at certain concentrations they were beneficial to the UV/H2O2 process. However, even with severe inhibitory effects, the decolorization efficiency of the UV/AA process was still several times higher than that of the UV/H2O2 process. The results are helpful for us to better understand the mechanisms behind the UV/AA process and may shed light on the application of UV-based advanced oxidation processes for wastewater treatment.

The fate of dichloroacetonitrile in UV/Cl2 and UV/H2O2 processes: implications on potable water reuse

This study investigated the fate of DCAN in UV/Cl2 and UV/H2O2 processes under the conditions relevant to potable water reuse (e.g., two pH values and three oxidant dosages). At pH 6 and an oxidant dosage of 500 μM, the degradation of DCAN in the UV/Cl2 process was attributed to UV photolysis (4.5%), HO−-assisted hydrolysis (10.5%), nucleophilic attack by ClO− (32.2%), and oxidation by radicals (i.e., HO˙ and Cl˙) (52.8%), while that in the UV/H2O2 process was mainly attributed to HO2− (32%) and HO˙ (48%). In both processes, the DCAN degradation rates were higher with increasing solution pH from 5 to 6, because the increased HO−-assisted hydrolysis and nucleophilic attack of DCAN surpassed the decreased radical oxidation of DCAN. The DCAN degradation was enhanced with increasing chlorine or H2O2 dosage from 100 to 1000 μM, mainly due to the increased contribution from the nucleophilic attack. DCAN was mostly transformed into dichloroacetic acid (DCAA) through different pathways in the two processes. At the same pH and oxidant dosage conditions, the degradation rates of DCAN in the UV/Cl2 process were higher than those in the UV/H2O2 process, due to the higher nucleophilic attack rates and radical oxidation rates in the former process. The cost of degrading 90% of DCAN using the UV/Cl2 process is about 1/8 of that using the UV/H2O2 process, making the UV/Cl2 process a more cost-effective UV-AOP in DCAN abatement for potable water reuse.

Wavelength-dependent chlorine photolysis and subsequent radical production using UV-LEDs as light sources

UV-LEDs are considered as the most promising UV light sources, because it has the potential to replace conventional UV lamps in some water treatment applications in the foreseeable future. In this study, UV-LEDs at four wavelengths in the UV-C or near UV-C range (i.e., 257.7, 268, 282.3, and 301.2 nm) were used to investigate the wavelength-dependency on chlorine photolysis and its subsequent radical formation. The fluence-based photodecay rates of hypochlorous acid (HOCl) and hypochlorite (OCl-) were monotonically correlated to their molar absorption coefficients and quantum yields, and the chlorine photodecay rates were much more significantly affected by molar absorption coefficients (β  = 0.949) than quantum yields (β  = 0.055). An empirical model that incorporated the chlorine photodecay rate constants, quantum yields, and molar absorption coefficients of HOCl and OCl- was established, validated and then used to predict the chlorine photodecay rate at any wavelength (257.7-301.2 nm) and pH (5-10). The modelling results suggested that the maximum fluence-based rate constant (1.46 × 10-4 m2 J-1) was obtained at 289.7 nm and pH 9.95. The wavelength dependency was larger at alkaline pH than at acidic pH, and the pH dependency was the largest at the longest wavelength. The formation of hydroxyl radicals (HO·) and reactive chlorine species (RCS) decreased with increasing wavelength at pH 6, and increased with increasing wavelength at pH 7. More HO· was formed at pH 6 than pH 7, but RCS showed the opposite pH-dependency. The findings in this study provide the fundamental information in selecting UV-LEDs with specific wavelength for enhancing/optimizing chlorine photodecay and/or its radical generation at different pHs in real-world applications.