Yulei Liu

Efficient degradation of atrazine by magnetic porous copper ferrite catalyzed peroxymonosulfate oxidation via the formation of hydroxyl and sulfate radicals

Magnetic porous copper ferrite (CuFe2O4) showed a notable catalytic activity to peroxymonosulfate (PMS). More than 98% of atrazine was degraded within 15 min at 1 mM PMS and 0.1 g/L CuFe2O4. In contrast, CuFe2O4 exhibited no obvious catalytic activity to peroxodisulfate or H2O2. Several factors affecting the catalytic performance of PMS/CuFe2O4 were investigated. Results showed that the catalytic degradation efficiency of atrazine increased with PMS and CuFe2O4 doses, but decreased with the increase of natural organic matters concentration. The catalytic oxidation also showed a dependence on initial pH. The presence of bicarbonate stimulated atrazine degradation by PMS/CuFe2O4 at low concentrations but inhibited the degradation at high concentrations. Furthermore, the reactive species for atrazine degradation in PMS/CuFe2O4 system were identified as hydroxyl radical (HO) and sulfate radical (SO4(·-)) through competition reactions of atrazine and nitrobenzene, instead of commonly used alcohol scavenging, which was not a reliable method in metal oxide catalyzed oxidation. Surface hydroxyl groups of CuFe2O4 were a critical part in radical generation and the copper on CuFe2O4 surface was an active site to catalyze PMS. The catalytic degradation of atrazine by PMS/CuFe2O4 was also effective under the background of actual waters.

Degradation of atrazine by UV/chlorine: Efficiency, influencing factors, and products

In this work, the degradation of atrazine by the combination of UV and chlorine (UV/chlorine) due to the formation of radicals during chlorine photolysis was systematically investigated in terms of efficiency, factors that influence the degradation kinetics, as well as oxidation products. It was found that the degradation efficiency of atrazine was enhanced by UV/chlorine compared to UV or chlorine alone. The degradation efficiency of atrazine was favorable at a lower pH, but was inhibited in the presence of natural organic matters. Meanwhile, the initial chlorine dosage, alkalinity, and chloride barely influenced the degradation efficiency under neutral pH conditions. The degradation of atrazine by UV/chlorine was inhibited in real waters (i.e., surface water and ground water) compared to in deionized water but was still more effective than UV alone. The oxidation products of atrazine resulting from de-alkylation, dechlorination-hydroxylation, alkylic-hydroxylation, alkylic-oxidation, alkylic-hydroxylation-dehydration, deamination-hydroxylation, and dechlorination-hydrogenation in UV/chlorine process were detected, which were slightly different from those formed in UV/H2O2 (commonly used UV-based advanced oxidation process). Particularly, the yields of three primary transformation products (desethyl-atrazine (DEA), desisopropyl-atrazine (DIA), and desethyl-desisopropyl-atrazine (DEIA)) were comparatively quantified in these two processes. The different trend of them formed in UV/chlorine system (DEA:DIA≈4) compared to that formed in UV/H2O2 system (DEA:DIA≈1) could be ascribed to the different reaction reactivities and mechanisms between HO• and Cl• with atrazine.

Anoxic biodegradation of triclosan and the removal of its antimicrobial effect in microbial fuel cells

Triclosan (TCS) is an emerging organic contaminant in the environment. Here, the anoxic bio-degradation of TCS in microbial fuel cells (MFCs) was explored. It was found that anoxic biodegradation of TCS could be achieved in MFC, and the removal rate of TCS was accelerated after reactor acclimation. After 7 months of operation, 10mg/L TCS could be removed within 8days in MFCs. Fluorescence microscopy results revealed that the microbe cells in the reactors were intact, and the microbes were in active state. Flow cytometry test showed that the proliferation of inoculated microbe was higher in MFC effluent than that in TCS solution. These data indicate that the biotoxicity of TCS has been largely eliminated after the treatment. The microbial community shift during the TCS degradation process was investigated as well. Species such as Geothrix, Corynebacterium, Sulfobacillus, GOUTA19, Geobacter, Acidithiobacillus and Acinetobacter, which were capable for the degradation of benzene-related and dechlorination of chlorine-containing chemicals, were flourished in the electrode biofilm. They may participate in the biodegradation of TCS. This work provides a new perspective for the anoxic biodegradation of recalcitrant organics, and can be useful for the in-situ bioremediation of environmental pollutants with the removal of their biotoxicity.

Comparative study on ferrate oxidation of BPS and BPAF: Kinetics, reaction mechanism, and the improvement on their biodegradability

Bisphenol S (BPS) and bisphenol AF (BPAF) were increasingly consumed and these compounds are resistant to environmental degradation. Herein, ferrate oxidation of BPS and BPAF was investigated, and biodegradability of the oxidation products was examined. The second-order reaction rate constants of ferrate with BPS and BPAF were 1.3 × 103 M-1s-1 and 3 × 102 M-1s-1, respectively, at pH 7.0, 25 °C. In the oxidation process, some BPS molecules dimerized, while other BPS molecules were oxidized through oxygen-transfer process, leading to the formation of hydroxylation products and benzene-ring cleavage products. The dominant reaction of BPAF with ferrate was oxygen-transfer process, and BPAF was degraded into lower molecular weight products. The variation of assimilable organic carbon (AOC) suggested that the biodegradability of BPAF and BPS was largely improved after ferrate oxidation. Compared with the BPS oxidation products, the BPAF oxidation products were easier to be bio-consumed. Pure culture test showed that BPAF inhibited the growth of Escherichia coli, while ferrate oxidation completely eliminated this toxic effect. Co-existing humic acid (HA, 1 mg C/L to 5 mg C/L) decreased the removal of BPS and BPAF with ferrate. Compared with BPAF, more oxidation intermediates formed in the ferrate oxidation of BPS may be reduced by HA to the parent molecular. Thus, the inhibition effect of HA on the ferrate oxidation of BPS was more obvious than that on BPAF.

Highly effective oxidation of roxarsone by ferrate and simultaneous arsenic removal with in situ formed ferric nanoparticles

Roxarsone (ROX) is used in breeding industry to prevent infection by parasites, stimulate livestock growth and improve pigmentation of livestock meat. After being released into environment, ROX could be bio-degraded with the formation of carcinogenic inorganic arsenic (As) species. Here, ferrate oxidation of ROX was reported, in which we studied total-As removal, determined reaction kinetics, identified oxidation products, and proposed a reaction mechanism. It was found that the apparent second-order rate constant (kapp) of ferrate with ROX was 305 M-1s-1 at pH 7.0, 25 °C, and over 95% of total As was removed within 10 min when ferrate/ROX molar ratio was 20:1. Species-specific rate constants analysis showed that HFeO4- was the dominant species reacting with ROX. Ferrate initially attacked AsC bond of ROX and resulted in the formation of arsenate and 2-nitrohydroquinone. The arsenate was simultaneously removed by ferric nanoparticles formed in the reduction of ferrate, while 2-nitrohydroquinone was further oxidized into nitro-1,4-benzoquinone. These results suggest that ferrate treatment can be an effective method for the control of ROX in water treatment.

Efficient oxidation and sorption of arsenite using a novel titanium(IV)-manganese(IV) binary oxide sorbent

Owing to the high toxicity and mobility, the removal of arsenite (As(III)) is significantly more difficult than arsenate (As(V)), thus representing a major challenge in arsenite-contaminated water treatment. For efficient elimination of As(III), we successfully fabricated a novel Ti-Mn binary oxide via a simultaneous oxidation and coprecipitation process. The amorphous oxide was aggregated from nanosized particles with a high specific surface area of 349.5 m2/g. It could effectively oxidize As(III) to As(V) and had a high As(III) sorption capacity of 107.0 mg/g. As(III) sorption occurred rapidly and equilibrium was achieved within 24 h. The kinetic data was well fitted by the pseudo-second-order equation, indicating a chemical sorption process. The material was almost independent upon the presence of competitive ions. The As(III) removal by the sorbent is a combined process coupled oxidation with sorption, where the MnO2 content is mainly responsible for oxidizing As(III) to As(V) and the formed As(V) is then adsorbed onto the surface of amorphous TiO2 content, through replacing the surface hydroxyl group or the adsorbed As(III) and forming inner-sphere surface complexes. Furthermore, the arsenic-containing oxide could be effectively regenerated and reused. The bi-functional sorbent could be used as a potentially attractive sorbent for As(III) removal in drinking water treatment and environmental remediation.