An EPR study on wastewater disinfection by peracetic acid,hydrogen peroxide and UV irradiation

EPR spectroscopy was applied to obtain qualitative and quantitative information on the radicals produced in disinfection processes of wastewater for agricultural reuse. The DEPMPO spin trap was employed to detect hydroxyl and carbon-centered short living radicals in two different peracetic acid solutions and a hydrogen peroxide solution used for water disinfection either in the absence or in the presence of UV-C irradiation. Moreover, three different kinds of water (wastewater, demineralized water, distilled water) were analysed in order to assess the contribution of Fenton reactions to the radical production. The spectroscopic results were discussed in relation to the efficiency of the different oxidizing agents and UV irradiation in wastewater disinfection evaluated as Escherichia Coli, Faecal and Total Coliforms inactivation.     

Introducing NH2 onto polymeric films via photo-induced C—H bond transformation with phenol derivatives as building blocks

A one-step process to introduce both the aromatic and aliphatic primary amino groups with high chemoselectivity was developed.Triplet state acetone abstracts the hydrogen atoms from both the C-H bond of the polymeric film substrate and the O-H bond of phenol which is the building block and the amino group carrier.As a result,two kinds of free radicals, confined carbon-centered chain radicals of the polymer substrate and mobile oxygen-centered phenoxy radicals,were generated.Then the C-O bonds were formed by the coupling reaction between these two kinds of free radicals.p-Tyramine and p-aminophenol were used as amino carriers.The successful introduction of amino groups onto LDPE,BOPP and PET film substrates was demonstrated by measurements of water contract angle（CA）,ultraviolet spectra（UV）,X-ray photoelectron spectroscopy（XPS） and fluorescent microscopy.The processing factors,such as the UV-light intensity and irradiation time,concentrations of p-tyramine and p-aminophenol,and the ratio of acetone/water were investigated.The optimized process parameters are as follows:UV light intensity 9500μW/cm²;irradiation time 18 min for BOPP and LDPE, 22 min for PET;the ratio of acetone/water = 1;and concentration of p-tyramine and p-aminophenol 15%for BOPP and LDPE,1%for PET.Based on the UV absorbance,the amino groups on the polymeric substrates were estimated to be in the range of 6.3×10^-6-9.5×10^-6 mmol/mm².     

Simultaneous Irradiation with Different Wavelengths of Ultraviolet Light has Synergistic Bactericidal Effect on Vibrio parahaemolyticus

Ultraviolet (UV) irradiation is an increasingly used method of water disinfection. UV rays can be classified by wavelength into UVA (320–400 nm), UVB (280‐320 nm), and UVC (<280 nm). We previously developed UVA sterilization equipment with a UVA light‐emitting diode (LED). The aim of this study was to establish a new water disinfection procedure using the combined irradiation of the UVA‐LED and another UV wavelength. An oxidative DNA product, 8‐hydroxy‐2’‐deoxyguanosine (8‐OHdG), increased after irradiation by UVA‐LED alone, and the level of cyclobutane pyrimidine dimers (CPDs) was increased by UVC alone in Vibrio parahaemolyticus. Although sequential irradiation of UVA‐LED and UVC‐induced additional bactericidal effects, simultaneous irradiation with UVA‐LED and UVC‐induced bactericidal synergistic effects. The 8‐OHdG and CPDs production showed no differences between sequential and simultaneous irradiation. Interestingly, the recovery of CPDs was delayed by simultaneous irradiation. The synergistic effect was absent in SOS response‐deficient mutants, such as the recA and lexA strains. Because recA‐ and lexA‐mediated SOS responses have crucial roles in a DNA repair pathway, the synergistic bactericidal effect produced by the simultaneous irradiation could depend on the suppression of the CPDs repair. The simultaneous irradiation of UVA‐LED and UVC is a candidate new procedure for effective water disinfection.     

Accelerated larvae development of Ascaris lumbricoides eggs with ultraviolet radiation

In order to investigate the effect of UV radiation on the development of Ascaris lumbricoides larvae, eggs were exposed to increasing UV doses. Filtered wastewater from the secondary effluent taken from the Damascus wastewater treatment plant (DWTP) was used as irradiation and incubation medium. The progressive and accelerated embryonation stages were microscopically observed and the percentages of completely developed larvae were determined weekly. Results indicated that the UV radiation accelerated the development of larvae with increasing UV dose. Preliminary information about the relationship between the UV radiation dose and rate of embryonation is also presented.     

Enhanced inactivation of Escherichia coli with Ag-coated TiO2 thin film under UV-C irradiation

The inactivation of Escherichia coli (E. coli) in water was investigated systematically with Ag-coated TiO₂ thin film under UV-C irradiation. Compared with UV-C irradiation alone, the inactivation of E. coli by the UV/Ag-TiO₂ process was enhanced and the photoreactivation of the bacteria was much repressed. Moreover, atomic force microscopy (AFM) measurements of E. coli showed that the presence of Ag-TiO₂ thin film during UV exposure could expedite the destruction of cell wall and cell membrane, which was further confirmed by the formation of malondialdehyde (MDA) and leakage of intracellular potassium ion (K⁺) and protein. The results suggest that the cell structure destruction might be the major reason for the enhancement of inactivation efficiency, and the prepared Ag-TiO₂ thin films show potential as a new improvement tool for UV-C disinfection.     

Comparison of the Disinfection Effects of Vacuum-UV (VUV) and UV Light on Bacillus subtilis Spores in Aqueous Suspensions at 172, 222 and 254 nm

The efficacy of UV and vacuum-UV (VUV) disinfection of Bacillus subtilis spores in aqueous suspensions at wavelengths of 172, 222 and 254 nm was evaluated. A Xe₂* excilamp, a KrCl* excilamp and a low-pressure mercury lamp were used as almost monochromatic light sources at these three wavelengths. The first-order inactivation rate constants at 172, 222 and 254 nm were 0.0023, 0.122 and 0.069 cm² mJ⁻¹, respectively. Therefore, a 2 log reduction of B .  subtilis spores was reached with fluences (UV doses) of 870, 21.6 and 40.4 mJ cm⁻² at these individual wavelengths. Consequently, for the inactivation of B .  subtilis spores, VUV exposure at 172 nm is much less efficient than exposure at the other two wavelengths, while exposure at 222 nm is more efficient than that at 254 nm, which is probably because triplet energy transfer from DPA to thymine bases at 222 nm is higher than that at 254 nm. This research indicated quantitatively that VUV light is not practicable for microorganism disinfection in water and wastewater treatment. However, in comparison with other advanced oxidation processes ( e.g. UV/TiO₂, UV/H₂O₂ or O₃/H₂O₂) the VUV-initiated photolysis of water is likely more efficient in generating hydroxyl radicals and more effective for the inactivation of microorganisms.     

Development and Optimization of Single Filament Plasma Jets for Wastewater Decontamination

New efficient depollution techniques for water decontamination, purification and disinfection are being sought to replace those classic methods (chemical, filtration, ozonisation, photochemical reactions) that have deficiency for some substances. The use of plasma technologies, discharges in, or in contact with, wastewater are promising approaches for the decomposition of pollutants by highly oxidative radicals, charged particles, UV radiation, etc. produced by plasma. In the present study we report on the potential of radiofrequency single and multiple filamentary Dielectric Barrier Discharge (DBD) jets for the decolorization of methylene blue (MB) dye in water solutions. Optical emission spectroscopy (OES) investigations were performed for the characterization of plasma evolving in air, and in liquid. The decolorization process was monitored by absorption spectroscopy. We determined the decolorization time, according to a variety of external parameters. The key parameters for obtaining the maximum decolorization rate were identified as being the discharge tube diameter, tube nature (glass/ceramic), the injected power in the discharge, the type of reactive gas and the number of filamentary plasma jets.

     

Identification of free radicals induced by UV irradiation in collagen water solutions

Electron paramagnetic resonance (EPR) method has shown that hydrogen atoms and acetic acid free radicals appear in surrounding acetic acid-water solution of collagen under ultraviolet (UV) irradiation. These free radicals interact with the collagen molecule; consequently, seven superfine components of EPR spectrum with the split of aH = 11.3G and g-factor 2.001 appear. It is assumed that this spectrum is related to the free radical occurred on the proline residue in collagen molecule. In order to discover .OH hydroxyl radicals even in minor concentration, spin trap 5.5-dimethyl-1-pyrroline N-oxide (DMPO) has been applied. During the irradiation of collagen water solution in the presence of spin trap, EPR spectrum of the DMPO/.OH adduct has not been identified, while the above mentioned spectrum has been observed once the hydrogen peroxide H2O2 and FeSO4 were added to the sample. That means that water photolysis does not take place in collagen water-solution due to UV irradiation. It was suggested that occurrence of hydrogen radical is connected with the electron transmission to the hydrogen ion. The possible source of free electrons can be aromatic residues, photo ionization of which takes place in collagen molecule due to UV irradiation.     

Role of Ozone in UV‐C Disinfection,Demonstrated by Comparison between Wild‐Type and Mutant Conidia of Aspergillus niger

This study aimed to investigate the tolerance of a melanized wild‐type strain of Aspergillus niger (CON1) and its light‐colored mutant (MUT1) to UV–C light and the concomitantly generated ozone. Treatments were segregated into four groups based on whether UV irradiation was used and the presence or absence of ozone: (?UV, ?O₃), (?UV, +O₃), (+UV, ?O₃) and (+UV, +O₃). The survival of CON1 and MUT1 conidia under +UV decreased as the exposure time increased, with CON1 showing greater resistance to UV irradiation than MUT1. Ozone induced CON1 conidium inactivation only under conditions of UV radiation exposure. While, the inactivation effect of ozone on MUT1 was always detectable regardless of the presence of UV irradiation. Furthermore, the CON1 conidial suspension showed lower UV light transmission than MUT1 when examined at the same concentration. Compared with the pigment in MUT1, the melanin in CON1 exhibited more potent radical‐scavenging activity and stronger UV absorbance. These results suggested that melanin protected A. niger against UV disinfection via UV screening and free radical scavenging. The process by which UV–C disinfection induces a continual decrease in conidial survival suggests that UV irradiation and ozone exert a synergistic fungicidal effect on A. niger prior to reaching a plateau.     

UV-C Peroxymonosulfate Activation for Wastewater Regeneration: Simultaneous Inactivation of Pathogens and Degradation of Contaminants of Emerging Concern

This study explores the capability of Sulfate Radical-based Advanced Oxidation Processes (SR-AOPs) for the simultaneous disinfection and decontamination of urban wastewater. Sulfate and hydroxyl radicals in solution were generated activating peroxymonosulfate (PMS) under UV-C irradiation at pilot plant scale. The efficiency of the process was assessed toward the removal of three CECs (Trimethoprim (TMP), Sulfamethoxazole (SMX), and Diclofenac (DCF)) and three bacteria (Escherichia coli, Enterococcus spp., and Pseudomonas spp.) in actual urban wastewater (UWW), obtaining the optimal value of PMS at 0.5 mmol/L. Under such experimental conditions, bacterial concentration ≤ 10 CFU/100 mL was reached after 15 min of UV-C treatment (0.03 kJ/L of accumulative UV-C radiation) for natural occurring bacteria, no bacterial regrowth was observed after 24 and 48 h, and 80% removal of total CECs was achieved after 12 min (0.03 kJ/L), with a release of sulfate ions far from the limit established in wastewater discharge. Moreover, the inactivation of Ampicillin (AMP), Ciprofloxacin (CPX), and Trimethoprim (TMP) antibiotic-resistant bacteria (ARB) and reduction of target genes (ARGs) were successfully achieved. Finally, a harmful effect toward the receiving aquatic environment was not observed according to Aliivibrio fischeri toxicity tests, while a slightly toxic effect toward plant growth (phytotoxicity tests) was detected. As a conclusion, a cost analysis demonstrated that the process could be feasible and a promising alternative to successfully address wastewater reuse challenges.     

Electrochemical disinfection – State of the art and tendencies

Electrochemical disinfection has gained increasing interest in many sectors of social and industrial life. The reason is the growing need to disinfect the air, water, and special surfaces of different nature such as drinking water, wastewater, pool water, and other water qualities or surfaces. New research studies are reported and discussed. A stronger orientation on engineering aspects is intended. Following tendencies can be identified - research on complex liquid systems, implementation of risks consideration seen from by-product formation, and better cooperation between researchers and industry oriented to improve cell design and disinfection technology. Partially, reaction kinetics is studied and discussed at higher levels of likelihood. Furthermore, it can be found that more and more research papers deal with hybrid technologies to create novelty, to use synergistic effects and to meet the demands of real system treatment under practical conditions. A major focus can be identified for wastewater treatment/disinfection emphasizing electrocoagulation and electro-photocatalysis.     

Photo-induced isomerization of three nitrotoluene isomers: A matrix-isolation infrared spectroscopic and quantum-chemical study

The photo-induced isomerization reactions of ortho-, meta- and para-nitrotoluene molecules were investigated by matrix isolation infrared spectroscopy and quantum chemical calculations. Under UV irradiation of ortho-nitrotoluene in solid argon, the hydrogen atom transfer isomer was formed, as reported previously. It was found that the hydrogen atom transfer isomer is unstable and rearranged to its nitro isomer upon annealing. In addition, the nitrite isomer as well as its dissociation product tolyloxy radical was also formed. Only the nitrite isomers and the tolyloxy radicals were formed upon UV excitation of the meta- and para-nitrotoluene molecules. Infrared spectra and vibrational frequency assignments of the newly observed nitrite isomers and tolyloxy radicals are reported, which are supported by quantum chemical calculations.     

PHOTOCHEMISTRY OF 2-MERCAPTOPYRIDINES. PART 3. EPR STUDY OF PHOTOPRODUCTION OF HYDROXYL RADICALS BY N-HYDROXYPYRIDINE-2-THIONE USING 5,5-DIMETHYL-1-PYRROLINE N-OXIDE IN AQUEOUS SOLUTIONS*

Abstract— N-Hydroxypyridine-2-thione, 2-S-PyrNOH, a potent antimicrobial, antifungal and anticancer agent, is photochemically active and upon UV irradiation generates free radicals. We have employed EPR and the spin-trap 5,5-dimethyl-l-pyrroline TV-oxide (DMPO) to investigate the photochemistry in aqueous solutions of 2-S-PyrNOH (used here in the form of a sodium salt, 2-S-PyrNONa). We found that upon photoactivation 2-S-PyrNONa can follow two different pathways: it can produce hydroxyl radicals and/or it can act as a photoreducing agent. The capacity of 2-S-PyrNONa to produce “OH” radicals has been demonstrated by: (1) EPR detection of the DMPO/OH adduct in UV-irradiated samples; (2) inhibition of the DMPO/OH formation by OH scavengers such as methyl alcohol, formate and DMSO and (3) by detection of EPR signals of DMPO adducts with radicals derived from reaction of OH with these inhibitors. The photoreductive capacity of 2-S-PyrNONa was deduced from the observation that the amplitude of the EPR signal of the spin adduct DMPO/OH decreased on UV irradiation in air-free pH 7.0 buffers and that the signal recovered in the dark and after aeration. The ability to generate free radicals upon UV irradiation suggests that 2-S-PyrNONa can be regarded as a potential photocytotoxic agent. This feature may be relevant to the biological action of this compound. Our findings also emphasize that caution should be used when 2-S-PyrNOH is employed as a source of OH radicals in biological or chemical systems.     

Formation of free radicals in water under high-power laser uv irradiation

It has been shown that under high-power laser UV irradiation (I = 10⁸–10¹⁰ W/cm², λ = 266 nm, τ_p = 30 ps) water becomes ionized by a two-photon mechanism to form some free radicals including the hydrated electron e^?_aq.     

A novel fiber optical device for ultraviolet disinfection of water

Since there are several problems in traditional UV disinfection techniques, a highly efficient, reliable and economical method, using quartz optical fibers to deliver UV light is proposed. The principle of the experimental setup is that ultraviolet rays are gathered by a reflector and converge on a light point, the diameter of approximately 5mm. In this way UV light can be transferred into water to kill the bacteria in the water. This paper presents preliminary results on water disinfection using this new UV disinfection setup. Its suitability for application could be shown in experiments with E. coli (ATCC8099) as test microorganisms. We have optimized the distribution of the optical fibers in the water in bench-scale study. This result can provide guidance for pilot-scale and field-scale study of this new technique. The results show that the new technique had a good performance under different conditions as follows: (a) turbidity level=10.2 NTU, (b) ferric ion concentration=0.3 mg/L, and (c) humic acid concentration=5 mg/L. The new technique provides a promising approach to disinfection treatment of drinking water.     

Photocatalytic disinfection of bacterial pollutants using suspended and immobilized TiO2 powders

The photocatalytic disinfection of Enterobacter cloacae and Enterobacter coli using microwave (MW), convection hydrothermal (HT) and Degussa P25 titania was investigated in suspension and immobilized reactors. In suspension reactors, MW‐treated TiO₂ was the most efficient catalyst (per unit weight of catalyst) for the disinfection of E. cloacae. However, HT‐treated TiO₂ was approximately 10 times more efficient than MW or P25 titania for the disinfection of E. coli suspensions in surface water using the immobilized reactor. In immobilized experiments, using surface water a significant amount of photolysis was observed using the MW‐ and HT‐treated films; however, disinfection on P25 films was primarily attributed to photocatalysis. Competitive action of inorganic ions and humic substances for hydroxyl radicals during photocatalytic experiments, as well as humic substances physically screening the cells from UV and hydroxyl radical attack resulted in low rates of disinfection. A decrease in colony size (from 1.5 to 0.3 mm) was noted during photocatalytic experiments. The smaller than average colonies were thought to occur during sublethal ^?OH and O₂^?? attack. Catalyst fouling was observed following experiments in surface water and the ability to regenerate the surface was demonstrated using photocatalytic degradation of oxalic acid as a model test system.     

UV-generated free radicals (FR) in skin: their prevention by sunscreens and their induction by self-tanning agents

In the past few years, the cellular effects of ultraviolet (UV) irradiation induced in skin have become increasingly recognized. Indeed, it is now well known that UV irradiation induces structural and cellular changes in all the compartments of skin tissue. The generation of reactive oxygen species (ROS) is the first and immediate consequence of UV exposure and therefore the quantitative determination of free radical reactions in the skin during UV radiation is of primary importance for the understanding of dermatological photodamage. The RSF method (radical sun protection factor) herein presented, based on electron spin resonance spectroscopy (ESR), enables the measurement of free radical reactions in skin biopsies directly during UV radiation. The amount of free radicals varies with UV doses and can be standardized by varying UV irradiance or exposure time. The RSF method allows the determination of the protective effect of UV filters and sunscreens as well as the radical induction capacity of self-tanning agents as dihydroxyacetone (DHA). The reaction of the reducing sugars used in self-tanning products and amino acids in the skin layer (Maillard reaction) leads to the formation of Amadori products that generate free radicals during UV irradiation. Using the RSF method three different self-tanning agents were analyzed and it was found, that in DHA-treated skin more than 180% additional radicals were generated during sun exposure with respect to untreated skin. For this reason the exposure duration in the sun must be shortened when self-tanners are used and photoaging processes are accelerated.     

二步法聚丙烯/丙烯酸表面接枝聚合研究

研究了二步法聚丙烯膜表面的丙烯酸接枝反应 .实验发现 ,以醋酐为溶剂的反应体系所得接枝率明显好于以水为溶剂的体系 ;接枝率随光敏剂浓度、单体浓度增大而增加 ;提高反应温度 ,可使接枝率明显增大 ;接枝后的聚丙烯膜表面亲水性可明显改善 .并用红外光谱证实了丙烯酸在聚丙烯膜表面的接枝 .     

EPR analysis of the interacting properties and the degradation over time and irradiation of mastic resin used for painting protection

Mastic resin used as a covering film for painting protection was analyzed by electron paramagnetic resonance (EPR) spectroscopy, both as received and upon aging in sun-light. The effect of prolonged exposure to sun-light was mimicked by UV and, more so, by xenon lamp irradiation. Solid mastic presented EPR signals due to radicals trapped by PBN in solution. Data in the literature indicated the formation of acyl radicals (RCO·). These radicals preferentially dissolved in medium polarity solvents. The radical concentration in the solid mastic increased over time more than 50 times upon UV irradiation for 96 h and, even more, by xenon irradiation for 800 h. Also the PBN-trapped radicals in solution increased in concentration by irradiation. Small nitroxide radicals (TEMPO) interacted with a polar fraction of mastic dissolved in methanol, but mainly interacted with low polar mastic molecules in hydrophobic solvents. It was suggested, on the basis of both the PBN-spin trapping data and the TEMPO mobility variation in the solvents at different polarities, that terpenoid molecules partially polymerize by a radical mechanism to form low molecular weight products. A polyaromatic-radical (pyrene-TEMPO) and a biomolecule-radical (doxylcholestane) both interact weakly with mastic molecules in cyclohexane solutions. A positively charged surfactant radical (dimethylammonium-TEMPO bromide) was easily adsorbed onto the solid mastic surface suggesting that detergents are responsible for mastic degradation. In conclusion, this study provided information on the degradation mechanism of mastic resin and on its interacting ability towards external molecules and pollutants.     

UV-induced free radicals in oriented DNA.

Abstract— Samples of oriented DNA containing 30% water were UV-irradiated at 77 K and investigated by electron paramagnetic resonance (EPR). The EPR spectra recorded in directions parallel and perpendicular to the DNA fibre direction showed that at low UV doses the induced free radicals are very similar to those induced by γ-irradiation at the same temperature. The γ-induced free radicals have previously been analysed and found to consist mainly of anionic free radicals on thymine and cationic free radicals on guanine. At higher UV doses or by suitable annealing of the samples given a low UV dose, significant amounts of hydrogen-addition radicals on thymine were observed. The quantum yield of free radical formation for irradiation at 300nm ± 10nm was estimated to 10^--⁴. We also made a quantitative determination of the UV-induced free radicals inside an optically effective volume of the sample. The following free radical induction frequencies at 77 K were estimated: γ-rays: 2 × 10^--¹² free radicals per rad per dalton and UV (300nm): 6 × 10^--¹² free radicals per J/m² per dalton.