A simple, nonhazardous, efficient and low energy-consuming process is desirable to generate powerful radicals from peroxymonosulfate (PMS) for recalcitrant pollutant removal. In this work, the ...production of radical species from PMS induced by a magnetic CuFe2O4 spinel was studied. Iopromide, a recalcitrant model pollutant, was used to investigate the efficiency of this process. CuFe2O4 showed higher activity and 30 times lower Cu2+ leaching (1.5 μg L–1 per 100 mg L–1) than a well-crystallized CuO at the same dosage. CuFe2O4 maintained its activity and crystallinity during repeated batch experiments. In comparison, the activity of CuO declined significantly, which was ascribed to the deterioration in its degree of crystallinity. The efficiency of the PMS/CuFe2O4 was highest at neutral pH and decreased at acidic and alkaline pHs. Sulfate radical was the primary radical species responsible for the iopromide degradation. On the basis of the stoichiometry of oxalate degradation in the PMS/CuFe2O4, the radical production yield from PMS was determined to be near 1 mol/mol. The PMS decomposition involved an inner-sphere complexation with the oxide’s surface Cu(II) sites. In situ characterization of the oxide surface with ATR-FTIR and Raman during the PMS decomposition suggested that surface Cu(II)–Cu(III)–Cu(II) redox cycle was responsible for the efficient sulfate radical generation from PMS.
Pharmaceuticals and personal care products (PPCPs) are a group of emerging micro-pollutants causing detrimental effects on living organisms even at low doses. Previous investigations have confirmed ...the presence of PPCPs in the environment at hazardous levels, mainly due to the inefficiency of conventional wastewater treatment plants (CWWTPs). Their stable structure induces longer persistence in the environment. Microalgae are currently used to bioremediate numerous pollutants of different characteristics and properties released from the domestic, industrial, agricultural, and farm sectors. CO2 mitigation during culture and the use of biomass as feedstock for biodiesel or biofuel production are, briefly, other benefits of microalgae-mediated treatment over CWWTPs. This review provides a comprehensive summary of recent literature, an overview of approaches and treatment systems, and breakthrough in the field of algal-mediated removal of PPCPs in wastewater treatment processes. The mechanisms involved in phycoremediation, along with their experimental approaches, have been discussed in detail. Factors influencing the removal of PPCPs from aqueous media are comprehensively described and assessed. A comparative study on microalgal strains is analyzed for a more efficient implementation of future processes. The role of microalgae to mitigate the most severe environmental impacts of PPCPs and the generation of antibiotic-resistant bacteria is discussed. Also, a detailed assessment of recent research on potential toxic effects of PPCPs on microalgae was conducted. The current review highlights microalgae as a promising and sustainable approach to efficiently bio-transform or bio-adsorb PPCPs.
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•Removal performances of PPCPs depend on the pollutant and microalgal species.•Immobilized microalgae are more efficient than suspended in removing PPCPs.•Acclimatization of microalgae is key to improve the removal performances of PPCPs.•Hybrid microalgae culture technique decreases PPCPs toxicity towards microalgae.
In this work, ceramic ultrafiltration membranes deposited with different metal oxides (i.e., TiO2, Fe2O3, MnO2, CuO, and CeO2) of around 10 nm in thickness and similar roughness were tested for O/W ...emulsion treatment. A distinct membrane fouling tendency was observed, which closely correlated to the properties of the filtration-layer metal oxides (i.e., surface hydroxyl groups, hydrophilicity, surface charge, and adhesion energy for oil droplets). Consistent with the distinct bond strength of the surface hydroxyl groups, hydrophilicity of these common metal oxides is quite different. The differences in hydrophilicity consequently lead to different adhesion of these metal oxides toward oil droplets, consistent with the irreversible membrane fouling tendency. In addition, the surface charge of the metal oxide opposite to that of emulsion can help to alleviate irreversible membrane fouling in ultrafiltration. Highly hydrophilic Fe2O3 with the lowest fouling tendency could be a potential filtration-layer material for the fabrication/modification of ceramic membranes for O/W emulsion treatment. To the best of our knowledge, this is the first study clearly showing the correlations between surface properties of filtration-layer metal oxides and ceramic membrane fouling tendency by O/W emulsion.
A sulfate radical-based advanced oxidation process (SR-AOP) has received increasing application interest for the removal of water/wastewater contaminants. However, limited knowledge is available on ...its side effects. This study investigated the side effects in terms of the production of total organic bromine (TOBr) and brominated disinfection byproducts (Br-DBPs) in the presence of bromide ion and organic matter in water. Sulfate radical was generated by heterogeneous catalytic activation of peroxymonosulfate. Isolated natural organic matter (NOM) fractions as well as low molecular weight (LMW) compounds were used as model organic matter. Considerable amounts of TOBr were produced by SR-AOP, where bromoform (TBM) and dibromoacetic acid (DBAA) were identified as dominant Br-DBPs. In general, SR-AOP favored the formation of DBAA, which is quite distinct from bromination with HOBr/OBr– (more TBM production). SR-AOP experimental results indicate that bromine incorporation is distributed among both hydrophobic and hydrophilic NOM fractions. Studies on model precursors reveal that LMW acids are reactive TBM precursors (citric acid > succinic acid > pyruvic acid > maleic acid). High DBAA formation from citric acid, aspartic acid, and asparagine was observed; meanwhile aspartic acid and asparagine were the major precursors of dibromoacetonitrile and dibromoacetamide, respectively.
Peroxydisulfate (PDS) is an appealing oxidant for contaminated groundwater and toxic industrial wastewaters. Activation of PDS is necessary for application because of its low reactivity. Present ...activation processes always generate sulfate radicals as actual oxidants which unselectively oxidize organics and halide anions reducing oxidation capacity of PDS and producing toxic halogenated products. Here we report that copper oxide (CuO) can efficiently activate PDS under mild conditions without producing sulfate radicals. The PDS/CuO coupled process is most efficient at neutral pH for decomposing a model compound, 2,4-dichlorophenol (2,4-DCP). In a continuous-flow reaction with an empty-bed contact time of 0.55 min, over 90% of 2,4-DCP (initially 20 μM) and 90% of adsorbable organic chlorine (AOCl) can be removed at the PDS/2,4-DCP molar ratio of 1 and 4, respectively. Based on kinetic study and surface characterization, PDS is proposed to be first activated by CuO through outer-sphere interaction, the rate-limiting step, followed by a rapid reaction with 2,4-DCP present in the solution. In the presence of ubiquitous chloride ions in groundwater/industrial wastewater, the PDS/CuO oxidation shows significant advantages over sulfate radical oxidation by achieving much higher 2,4-DCP degradation capacity and avoiding the formation of highly chlorinated degradation products. This work provides a new way of PDS activation for contaminant removal.
Schematic diagram of MDZ removal in Chlorella vulgaris culture.
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•Metronidazole is efficiently removed during algal treatment.•Metronidazole is removed via sorption onto the ...biomass.•Metronidazole showed toxicity to C. vulgaris at stationary phase of life cycle.•The removal efficiency of C. vulgaris decreased with increase of antibiotic.
This current study investigated the removal of metronidazole from aqueous media by C. vulgaris. Two different initial sizes of inoculum (0.05 and 0.5 g L−1) were tested for a wide concentration range of metronidazole (1–50 μM). The effect of metronidazole concentrations on biomass production was studied for 20 days. The exopolymeric substances (EPS) were quantified and correlated with the removal of antibiotics from aqueous media. Specifically, MDZ stimulated the production of EPS in C. vulgaris, which played the major role in the adsorption of this antibiotic. Also, metronidazole significantly influenced the zeta potential of C. vulgaris in the test cultures, indicating a change in surface characteristics. This decrease in surface negative charge caused auto-flocculation phenomena at a stationary phase. Chronic and acute toxicity experiments showed that metronidazole was harmful to C. vulgaris at stationary phase. Results from this study would advance our knowledge on the treatment of metronidazole-contaminated waters with C. vulgaris as a green technology-oriented process.
Previous studies showed that significant bromate (BrO3 –) can be formed via the CuO-catalyzed disproportionation of hypobromous acid (HOBr) pathway. In this study, the influence of CuO on the ...formation of BrO3 – and halogenated disinfection byproducts (DBPs) (e.g., trihalomethanes, THMs and haloacetic acids, HAAs) during chlorination of six dissolved organic matter (DOM) isolates was investigated. Only in the presence of slow reacting DOM (from treated Colorado River water, i.e., CRW-BF-HPO), significant BrO3 – formation is observed, which competes with bromination of DOM (i.e., THM and HAA formation). Reactions between HOBr and 12 model compounds in the presence of CuO indicates that CuO-catalyzed HOBr disproportionation is completely inhibited by fast reacting phenols, while it predominates in the presence of practically unreactive compounds (acetone, butanol, propionic, and butyric acids). In the presence of slow reacting di- and tricarboxylic acids (oxalic, malonic, succinic, and citric acids), BrO3 – formation varies, depending on its competition with bromoform and dibromoacetic acid formation (i.e., bromination pathway). The latter pathway can be enhanced by CuO due to the activation of HOBr. Therefore, increasing CuO dose (0–0.2 g L–1) in a reaction system containing chlorine, bromide, and CRW-BF-HPO enhances the formation of BrO3 –, total THMs and HAAs. Factors including pH and initial reactant concentrations influence the DBP formation. These novel findings have implications for elevated DBP formation during transportation of chlorinated waters in copper-containing distribution systems.
EfOM has been regarded as a major organic foulant resulting in UF membrane fouling in wastewater reclamation. To investigate fouling potential of different EfOM fractions, the present study isolated ...EfOM into hydrophobic neutrals (HPO-N), colloids, hydrophobic acids (HPO-A), transphilic neutrals and acids (TPI), and hydrophilics (HPI), and tested their fouling effect in both salt solution and pure water during ultrafiltration (UF). Major functional groups and chemical structure of the isolates were identified using Fourier transform infrared spectroscopy (FT-IR) and solid-state carbon nuclear magnetic resonance ((13)C NMR) analysis. The influence of the isolation process on the properties of EfOM fractions was minor because the raw and reconstituted secondary effluents were found similar with respect to UV absorbance, molecular size distribution, and fluorescence character. In membrane filtration tests, unified membrane fouling index (UMFI) and hydraulic resistance were used to quantify irreversible fouling potential of different water samples. Results show that under similar DOC level in feed water, colloids present much more irreversible fouling than other fractions. The fouling effect of the isolates is related to their size, chemical properties, and solution chemistry. Further investigations have identified that the interaction between colloids and other fractions also influences the performance of colloids in fouling phenomena.
This study investigated the degradation and deactivation of an extracellular ampicillin resistance gene (ampR) encoded in plasmid pUC19 during exposure to UV254, •OH (generated by UV>290/H2O2), and ...combined exposure to UV254 and •OH (and/or SO4•−) using UV254/H2O2 and UV254/S2O82−. The degradation rates of ampR measured by quantitative polymerase chain reaction increased with increasing target amplicon length (192–851 bps). The rate constants for the degradation of pUC19 (2686 bps) were calculated as 0.26 cm2/mJ for UV254 and 1.5 × 1011 M−1s−1 for •OH, based on the degradation rates of ampR amplicons and assuming an equal sensitivity of DNA damage across the entire plasmid. DNA repair-proficient Escherichia coli (E. coli) AB1157 strain (wild-type) and its repair-deficient mutants including AB1886 (uvrA−), AB2463 (recA−), AB2480 (uvrA−, recA−), and DH5α (recA−, endA−) were applied as recipient cells in gene transformation assays. Results suggested that the elimination efficiency of transforming activity during UV254 and •OH exposure was dependent on the type of DNA repair genes in recipient E. coli strains. Losses of transforming activity were slower than the degradation of pUC19 by a factor of up to ∼5 (for E. coli DH5α), highlighting the importance of DNA repair in recipient cells. The degradation rates of ampR amplicons were much larger (by a factor of ∼4) in UV254/H2O2 and UV254/S2O82− than UV254 direct photolysis, indicating the significant contribution of •OH and SO4•− to the gene degradation. Not only UV254 and SO4•−, but also •OH contributed to the degradation of ampR during UV254/S2O82−, which was attributed to the conversion of SO4•− to •OH and a 10-fold larger reactivity of •OH towards ampR as compared to SO4•−. However, the enhanced gene degradation by radicals did not lead to a faster elimination of gene transforming activity during UV254/H2O2 and UV254/S2O82−, suggesting that UV254- and radical-induced DNA damage were not additive in their contributions to losses of gene transforming activity. Wastewater effluent organic matter (EfOM) accelerated the degradation of ampR during UV254 irradiation by means of reactive species production through indirect photolysis reactions, whereas EfOM mainly acted as a radical scavenger during UV254/H2O2 and UV254/S2O82− treatments.
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•Degradation and deactivation kinetics of a plasmid-encoded resistance gene (ampR).•Individual vs combined effect of UV254 and radicals (•OH, SO4•−) on ampR•Slower gene deactivation rate than the plasmid degradation due to DNA damage repair.•UV- and radical-induced DNA damage are not additive in causing gene deactivation.•Effluent organics as photo-sensitizers or radical scavengers for ampR degradation.
A recent investigation has demonstrated that peroxymonosulfate (PMS), a peroxide commonly applied as a radical precursor during advanced oxidation processes (AOPs), can degrade organic contaminants ...without the involvement of radicals. However, little is known about this non-radical reaction mechanism. In this study, the reactivity of PMS with several nitrogenous compounds was investigated. Fluoroquinolone antibiotics (except for flumequine) were rapidly degraded by direct PMS oxidation, followed by aliphatic amines (e.g., metoprolol and venlafaxine) and nitrogenous heterocyclic compounds (e.g., adenine and caffeine) at pH 8. The degradation rate of fluoroquinolones followed a second-order kinetic and was highly pH and structure-dependent. Unlike the radical-based AOPs, the direct degradation of contaminants by PMS was less influenced by the scavenging effect of the water matrix. High-Resolution Mass Spectrometry (HRMS) analysis demonstrated that the piperazine ring of fluoroquinolones was the main reaction site. Results showed that the direct electron-transfer from nitrogenous moieties (piperazine ring) to PMS can produce amide and aldehyde compounds. An amide-containing transformation product of ciprofloxacin (m/z 320), showing the highest signal intensity on HRMS, was previously recorded during ozonation. Moreover, the hydroxylamine analogue of ciprofloxacin and enrofloxacin N-oxide were tentatively identified, and the formation of the latter was not impacted by the dissolved oxygen in water. These results suggested that PMS also reacts with nitrogenous compounds via oxygen transfer pathway. Agar disk-diffusion tests indicated that PMS treatment efficiently removed the antibacterial activity of ciprofloxacin with the complete degradation of parent antibiotic, except for the transformation products in an earlier stage, which might still exert antibacterial potency.
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•The reactivity of peroxymonosulfate with nitrogenous compounds were compared.•A product with an amide group had the highest intensity on mass spectrometry.•N-oxide was tentatively identified from enrofloxacin.•Reaction mechanism includes the electron and oxygen transfer pathways.•Ciprofloxacin by-products in earlier stages exerted antibacterial potency.