Oxygen vacancies-dominated reactive species generation from peroxymonosulfate activated by MoO3-x for pollutant degradation.

Interface oxygen vacancies (OVs) are commonly used to improve the catalytic performance of activators in persulfate-based advanced oxidation processes, but the underlying mechanism was not fully explored. This work reports a facile heat treatment method to regulate OVs in MoO3-x to elucidate the mechanism of peroxymonosulfate (PMS) activated by OVs to degrade 2,4,4-Trichlorobiphenyl (PCB28). Electron spin resonance, free radical quenching, X-ray photoelectron spectroscopy, and Raman spectroscopy confirmed that both reducing Mo species and OVs of MoO3-x surface were responsible for PMS activation. Further experiments and Density Function Theory (DFT) calculation suggest that OVs in MoO3-x induced the formation of superoxide radical (O2•-), and then O2•- was transformed into singlet oxygen (1O2) or mediated PMS activation to generate radicals, which contritbued to 70.2% of PCB28 degradation. The steady-state concentrations of free radical calculated with the kinetics model show that OVs were more favorable to mediate PMS to generate hydroxyl radicals (•OH) under oxic conditions, while reducing Mo species would like to induce PMS to produce sulfate radicals (SO4•-). Overall, this study is dedicated to a new insight into the in-depth mechanism of PMS activation by OVs-rich catalysts and provides a novel strategy for reactive species regulation in PMS based oxidation process.

Oxytetracycline induced the redox of iron and promoted the oxidation of As(III).

Antibiotics and arsenic are two frequently detected contaminants in soils and waters, both of which have potential threats to human health. There are few studies focusing on the interaction between these two groups of contaminants in the environment. In this study, we found that the presence of oxytetracycline could significantly promote the oxidation of inorganic As(III) to As(V) with trace Fe(III) (10 µM) and H2O2 (100 µM) at near natural pH, and OTC was degraded simultaneously. The most possible mechanism was that OTC could complex with Fe(III) and reduce Fe(III) to Fe(II), which further induced the Fenton-like reaction. Furthermore, structural Fe(III) of α-FeOOH and adsorbed Fe(III) of montmorillonite could also induce these reactions, and the oxidation rate of As(III) was higher with Fe(III)-montmorillonite than aqueous Fe(III). Based on this study, the transformation of As(III) and OTC could occur in four natural water samples, including river water, groundwater and livestock wastewaters. The results of this study revealed the overlooked effect of residual tetracyclines antibiotics on the transformation of co-existing As(III) in natural waters and soils, which might greatly reduce the toxicity of As(III) in the environment.

Two transformation pathways of Acetaminophen with Fe3+ saturated clay particles in dark or light.

Acetaminophen (AP) has been frequently detected in different environments due to its wide usage as a common analgesic and antipyretic pharmaceutical. Excess residual of AP in the environment may cause biological risk. However, information about its environmental behaviors was limited, especially the interactions with clay minerals. In this study, AP transformation mediated by Fe3+ saturated clay particles was systematically investigated. The results showed 47.6 ± 1.1% or 78.9 ± 0.5% of AP was removed in the presence of Fe3+-montmorillonite respectively in dark or under simulated sunlight irradiation after 10 h. The hypothesized mechanism was that exchangeable ferric ions can either obtain electron from AP to form AP radical, or produce •OH under light, which can further react with AP. In dark condition, AP radicals could cross-couple with each other to form dimers, while oxidation products were also detected under light irradiation due to •OH attacking. Moreover, higher concentration of dissolved oxygen (DO) facilitated Fe3+ regeneration on clay surfaces and more reactive Fe species distributed in lower pH, which could significantly enhance the removal of AP both in dark and light. Results of this study revealed that clay minerals played important roles in the abiotic transformation of AP either in dark or under light irradiation, and oligomerization other than mineralization were the dominant processes.

Efficient activation of peroxymonosulfate by copper sulfide for diethyl phthalate degradation: Performance, radical generation and mechanism.

Copper-containing minerals have been extensively used in Fenton-like processes for degradation of pollutants and have exhibited great potential for environmental remediation. This work reports the first use of copper sulfide (CuS), a typical Cu-mineral, for the activation of peroxymonosulfate (PMS) for pollutant degradation; the study also elucidates the underlying mechanism of these processes. Copper sulfide effectively activated PMS to degrade diethyl phthalate (DEP). Electron paramagnetic resonance, free radical quenching, X-ray photoelectron spectroscopy, X-ray diffraction analyses and DFT calculations confirmed that ≡Cu (I)/≡Cu (II) cycling on the surface of CuS provided the main pathway to activate PMS to produce highly oxidative species. Unlike conventional sulfate radical-based PMS activation processes, hydroxyl radical (•OH) were found to be the dominant radical in the tested CuS/PMS system, which performed more efficiently than an alternative •OH-based oxidation system (CuS/H2O2) for DEP degradation. In addition, the presence of anions such Cl- and NO3- has limited inhibition effects on DEP degradation. Overall, this study provides an efficient pathway for PMS-based environmental remediation as well as a new insight into the mechanism of PMS activation by Cu-containing minerals.

Simultaneous immobilization of cadmium and lead in contaminated soils by hybrid bio-nanocomposites of fungal hyphae and nano-hydroxyapatites.

Self-aggregation of bulk nano-hydroxyapatites (n-HAPs) undermines their immobilization efficiencies of heavy metals in the contaminated soils. Here, the low-cost, easily obtained, and environment-friendly filamentous fungi have been introduced for the bio-matrices of the hybrid bio-nanocomposites to potentially solve such problem of n-HAPs. According to SEM, TEM, XRD, and FT-IR analyses, n-HAPs were successfully coated onto the fungal hyphae and their self-aggregation was improved. The immobilization efficiencies of diethylene-triamine-pentaacetic acid (DTPA)-extractable Cd and Pb in the contaminated soils by the bio-nanocomposites were individually one to four times of that by n-HAPs or the fungal hyphae. Moreover, the Aspergillus niger-based bio-nanocomposite (ANHP) was superior to the Penicillium Chrysogenum F1-based bio-nanocomposite (PCHP) in immobilization of Cd and Pb in the contaminated soils. In addition, the results of XRD showed that one of the potential mechanisms of metal immobilization by the hybrid bio-nanocomposites was dissolution of n-HAPs followed by precipitation of new metal phosphate minerals. Our results suggest that the hybrid bio-nanocomposite (ANHP) can be recognized as a promising soil amendment candidate for effective remediation on the soils simultaneously contaminated by Cd and Pb.