Rapid degradation of tetracycline hydrochloride by heterogeneous photocatalysis coupling persulfate oxidation with MIL-53(Fe) under visible light irradiation.

This work demonstrates a facile route to assemble MIL-53(Fe) by solvothermal method. Sulfate radical-based advanced oxidation processes (SR-AOPs) coupling with photocatalysis based on MIL-53(Fe) were investigated under visible light. The catalytic effect of MIL-53(Fe) for the degradation of tetracycline hydrochloride (TC-HCl) was systematically studied, as well as the reusability of the catalyst and the effect of operating parameters. The results indicated that 99.7 % of TC (300 mg/L) could be degraded within 80 min in the SR-AOPs coupling with photocatalysis processes, as compared to 71.4 % for the SR-AOPs and only 17.1 % for the photocatalysis. The trapping experiments and electron spin-resonance spectroscopy (ESR) showed the photogenerated electrons of MIL-53(Fe) under visible light irritation were trapped by persulfate to generated sulfate radicals which effectively suppressed the recombination of photogenerated carriers. And also, the SO4- could be formed by the conversion between Fe (Ⅲ) and Fe (Ⅱ) in MIL-53(Fe). Moreover, OH and O2- generated by the reaction increased significantly due to the increase of SO4- which generated more OH and reduced photogenerated carrier recombination respectively. Thus, the degradation efficiency of TC-HCl was improved. Furthermore, the degradation pathway for TC-HCl was proposed using the theoretical calculations and liquid chromatography coupled with mass spectrometry.

Degradation of imidacloprid by UV-activated persulfate and peroxymonosulfate processes: Kinetics, impact of key factors and degradation pathway.

UV-activated persulfate (UV/PS) and peroxymonosulfate (UV/PMS) processes as alternative methods for removal of imidacloprid (IMP) were conducted for the first time. The reaction rate constants between IMP and the sulfate or hydroxyl radical were calculated as 2.33×109  or 2.42×1010 M-1 s-1, respectively. The degradation of IMP was greatly improved by UV/PS and UV/PMS compared with only UV or oxidant. At any given dosage, UV/PS achieved higher IMP removal rate than UV/PMS. The pH range affecting the degradation in the UV/PS and UV/PMS systems were different in the ranges of 6-8 and 9 to 10. SO42-, F- and NO3- had no obvious effect on the degradation in the UV/PS and UV/PMS systems. CO32- and PO43- inhibited the degradation of IMP in the UV/PS system, while they enhanced the degradation in the UV/PMS system. Algae organic matters (AOM) were used to consider the impact of the degradation of IMP for the first time. The removal of IMP were restrained by both AOM and natural organic matters. The higher removal rate of IMP demonstrated that both UV/PS and UV/PMS were suitable for treating the water containing IMP, while UV/PS was cost-effective than UV/PMS based on the total cost calculation. Finally, the degradation pathways of IMP were proposed.

Photodegradation of sulfasalazine and its human metabolites in water by UV and UV/peroxydisulfate processes.

The widespread occurrence of pharmaceuticals and their metabolites in natural waters has raised great concerns about their potential risks on human health and ecological systems. This study systematically investigates the degradation of sulfasalazine (SSZ) and its two human metabolites, sulfapyridine (SPD) and 5-aminosalicylic acid (5-ASA), by UV and UV/peroxydisulfate (UV/PDS) processes. Experimental results show that SPD and 5-ASA were readily degraded upon UV 254 nm direct photolysis, with quantum yields measured to be (8.6 ±â€¯0.8) × 10-3 and (2.4 ±â€¯0.1) × 10-2 mol Einstein-1, respectively. Although SSZ was resistant to direct UV photolysis, it could be effectively removed by both UV/H2O2 and UV/PDS processes, with fluence-based pseudo-first-order rate constants determined to be 0.0030 and 0.0038 cm2 mJ-1, respectively. Second-order rate constant between SO4•- and SSZ was measured as (1.33 ±â€¯0.01) × 109 M-1s-1 by competition kinetic method. A kinetic model was established for predicting the degradation rate of SSZ in the UV/PDS process. Increasing the dosage of PDS significantly enhanced the degradation of SSZ in the UV/PDS process, which can be well predicted by the developed kinetic model. Natural water constituents, such as natural organic matter (NOM) and bicarbonate (HCO3-), influenced the degradation of SSZ differently. The azo functional group of SSZ molecule was predicted as the reactive site susceptible to electrophilic attack by SO4•- by frontier electron densities (FEDs) calculations. Four intermediate products arising from azo bond cleavage and SO2 extrusion were identified by solid phase extraction-liquid chromatography-triple quadrupole mass spectrometry (SPE-LC-MS/MS). Based on the products identified, detailed transformation pathways for SSZ degradation in the UV/PDS system were proposed. Results reveal that UV/PDS could be an efficient approach for remediation of water contaminated by SSZ and its metabolites.

Applying ultraviolet/persulfate (UV/PS) pre-oxidation for controlling ultrafiltration membrane fouling by natural organic matter (NOM) in surface water.

Membrane fouling is a recognized obstacle for the application of ultrafiltration (UF) for drinking water treatment. In this study, ultraviolet/persulfate (UV/PS) oxidation was employed as a pretreatment to control membrane fouling caused by natural organic matter (NOM) in surface water. The effects of UV/PS pretreatment on amounts and characteristics of NOM were investigated in terms of dissolved organic carbon, fluorescent spectrum, molecular weight distribution and hydrophobicity. UF membrane fouling during filtration of raw and pre-oxidized water was compared with transmembrane pressure development, and the fouled membranes were further characterized using scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The results indicate that NOM was considerably degraded and partially mineralized (∼58%) by UV/PS pretreatment at a PS dose not exceeding 0.6 mM and a UV irradiation time within 120 min, which was attributed to the generation of sulfate and hydroxyl radicals. The fluorescent compounds in NOM were almost completely degraded (>98%) by the UV/PS pretreatment at a PS dose of 0.4 mM, except for tyrosine-like proteins (∼80%). Moreover, UV/PS pretreatment decreased the ratio of macromolecular compounds and increased the hydrophilic fractions, resulting in reduced NOM adhesion to the membrane. Hence, irreversible fouling by NOM was significantly retarded (∼75%) by the UV/PS pretreatment due to reduction in NOM, and more importantly by preferential degradation of fluorescent, macromolecular and hydrophobic compounds. Fouling control performance was considerably improved at increased PS doses and extended UV irradiation time.

Kinetics and mechanism investigation on the destruction of oxytetracycline by UV-254nm activation of persulfate.

Oxytetracycline (OTC), an important broad-spectrum antibiotic, has been detected extensively in various environmental systems, which may have a detrimental impact on ecosystem and human health through the development of drug resistant bacteria and pathogens. In this study, the degradation of OTC was evaluated by UV-254nm activated persulfate (PS). The observed UV fluence based pseudo first-order rate constant (kobs) was found to be the highest at near neutral pH conditions (pH 5.5-8.5). Presence of various natural water constituents had different effects on OTC degradation, with a significant enhancement in the presence of bicarbonate or Cu(2+). Limited elimination of total organic carbon (TOC) and PS was observed during the mineralization of OTC. Transformation byproducts in the presence and absence of hydroxyl radical scavenging agent tert-butanol (t-BuOH) were identified using ultra-high definition accurate-mass quadrupole time-of-flight liquid chromatography/mass spectrometer (LC-QTOF/MS). Potential OTC degradation mechanism was subsequently proposed revealing four different reaction pathways by SO4(-) reaction including hydroxylation (+16Da), demethylation (-14Da), decarbonylation (-28Da) and dehydration (-18Da). This study suggests that UV-254nm/PS is a promising treatment technology for the control of water pollution caused by emerging contaminants such as OTC.

Mechanistic study of photo-oxidation of Bisphenol-A (BPA) with hydrogen peroxide (H2O2) and sodium persulfate (SPS).

The removal of Bisphenol-A (BPA) from contaminated water using advanced oxidation methods such as UV-C assisted oxidation by hydrogen peroxide (H2O2) and sodium persulfate (SPS) has been reported by the authors earlier (Sharma et al., 2015a). In the present study, the authors report the removal of BPA from aqueous solution by the above two methods and its degradation mechanism. UV-C light (254 nm wavelength, 40 W power) was applied to BPA contaminated water at natural pH (pHN) under room temperature conditions. Experiments were carried out with the initial BPA concentration in the range of 0.04 mM-0.31 mM and the oxidant/BPA molar ratio in the range of 294:1-38:1 for UV-C/H2O2 and 31.5-4.06:1 for UV-C/SPS systems. The removal of BPA enhanced with decreasing BPA concentration. The total organic carbon also decreased with the UV-C irradiation time under optimum conditions ([H2O2]0 = 11.76 mM; [SPS]0 = 1.26 mM; temperature (29 ± 3 °C). Competition of BPA for reaction with HO or [Formula: see text] radicals at its higher concentrations results in a decrease in the removal of BPA. The intermediates with smaller and higher molecular weights than that of BPA were found in the treated water. Based on GC-MS and FTIR spectra of the reaction mixture, the formation of hydroxylated by-products testified the HO mediated oxidation pathway in the BPA degradation, while the formation of quinones and phenoxy phenols pointed to the [Formula: see text] dominating pathway through the formation of hydroxycyclohexadienyl (HCHD) and BPA phenoxyl radicals. The main route of BPA degradation is the hydroxylation followed by dehydration, coupling and ring opening reactions.

Degradation and mineralization of Bisphenol A (BPA) in aqueous solution using advanced oxidation processes: UV/H2O2 and UV/S2O8(2-) oxidation systems.

This work reports on the removal and mineralization of an endocrine disrupting chemical, Bisphenol A (BPA) at a concentration of 0.22 mM in aqueous solution using inorganic oxidants (hydrogen peroxide, H2O2 and sodium persulfate, Na2S2O8;S2O8(2-)) under UV irradiation at a wavelength of 254 nm and 40 W power (Io = 1.26 × 10(-6) E s(-1)) at its natural pH and a temperature of 29 ± 3 °C. With an optimum persulfate concentration of 1.26 mM, the UV/S2O8(2-) process resulted in ∼95% BPA removal after 240 min of irradiation. The optimum BPA removal was found to be ∼85% with a H2O2 concentration of 11.76 mM. At higher concentrations, either of the oxidants showed an adverse effect because of the quenching of the hydroxyl or sulfate radicals in the BPA solution. The sulfate-based oxidation process could be used over a wider initial pH range of 3-12, but the hydroxyl radical-based oxidation of BPA should be carried out in the acidic pH range only. The water matrix components (bicarbonate, chloride and humic acid) showed higher scavenging effect in hydroxyl radical-based oxidation than that in the sulfate radical-based oxidation of BPA. UV/S2O8(2-) oxidation system utilized less energy (307 kWh/m(3)) EE/O in comparison to UV/H2O2 system (509 kWh/m(3)) under optimum operating conditions. The cost of UV irradiation far outweighed the cost of the oxidants in the process. However, the total cost of treatment of persulfate-based system was much lower than that of H2O2-based oxidation system.

Degradation kinetics and mechanism of ß-lactam antibiotics by the activation of H2O2 and Na2S2O8 under UV-254nm irradiation.

The extensive production and usage of antibiotics have led to an increasing occurrence of antibiotic residuals in various aquatic compartments, presenting a significant threat to both ecosystem and human health. This study investigated the degradation of selected ß-lactam antibiotics (penicillins: ampicillin, penicillin V, and piperacillin; cephalosporin: cephalothin) by UV-254nm activated H2O2 and S2O8(2-) photochemical processes. The UV irradiation alone resulted in various degrees of direct photolysis of the antibiotics; while the addition of the oxidants improved significantly the removal efficiency. The steady-state radical concentrations were estimated, revealing a non-negligible contribution of hydroxyl radicals in the UV/S2O8(2-) system. Mineralization of the ß-lactams could be achieved at high UV fluence, with a slow formation of SO4(2-) and a much lower elimination of total organic carbon (TOC). The transformation mechanisms were also investigated showing the main reaction pathways of hydroxylation (+16Da) at the aromatic ring and/or the sulfur atom, hydrolysis (+18Da) at the ß-lactam ring and decarboxylation (-44Da) for the three penicillins. Oxidation of amine group was also observed for ampicillin. This study suggests that UV/H2O2 and UV/S2O8(2-) advanced oxidation processes (AOPs) are capable of degrading ß-lactam antibiotics decreasing consequently the antibiotic activity of treated waters.

Efficient chemical and visible-light-driven water oxidation using nickel complexes and salts as precatalysts.

Chemical and visible-light-driven water oxidation catalyzed by a number of Ni complexes and salts have been investigated at pH 7-9 in borate buffer. For chemical oxidation, [Ru(bpy)3](3+) (bpy = 2,2'-bipyridine) was used as the oxidant, with turnover numbers (TONs) >65 and a maximum turnover frequency (TOFmax) >0.9 s(-1). Notably, simple Ni salts such as Ni(NO3 )2 are more active than Ni complexes that bear multidentate N-donor ligands. The Ni complexes and salts are also active catalysts for visible-light-driven water oxidation that uses [Ru(bpy)3](2+) as the photosensitizer and S2 O8 (2-) as the sacrificial oxidant; a TON>1200 was obtained at pH 8.5 by using Ni(NO3)2 as the catalyst. Dynamic light scattering measurements revealed the formation of nanoparticles in chemical and visible-light-driven water oxidation by the Ni catalysts. These nanoparticles aggregated during water oxidation to form submicron particles that were isolated and shown to be partially reduced ß-NiOOH by various techniques, which include SEM, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, XRD, and IR spectroscopy. These results suggest that the Ni complexes and salts act as precatalysts that decompose under oxidative conditions to form an active nickel oxide catalyst. The nature of this active oxide catalyst is discussed.

Examination of femtosecond laser matter interaction in multipulse regime for surface nanopatterning of vitreous substrates.

The paper presents our results on laser micro- and nanostructuring of sodium aluminosilicate glass for the permanent storage purposes and photonics applications. Surface structuring is realized by fs laser irradiation followed by the subsequent etching in a potassium hydroxide (10M@80 °C) for 1 to 10 minutes. As the energy deposited is lower than the damage and/or ablation threshold, the chemical etching permits to produce small craters in the laser modified region. The laser parameters dependent interaction regimes are revealed by microscopic analysis (SEM and AFM). The influence of etching time on craters formation is investigated under different incident energies, number of pulses and polarization states.

Chemical and optical control of peristaltic actuator based on self-oscillating porous gel.

We demonstrate the chemical and optical control of the self-sustaining peristaltic motion of a structural colored porous hydrogel.