Photolysis behavior of herbicide propisochlor in water media and preliminary analysis of photoproducts under different light sources

Photolysis behavior of a new herbicide propisochlor in water media as well as the effects of light sources, initial concentration of propisochlor, pH value, dissolved oxygen (DO) level, and salinity on the photolysis process was investigated. It was found that the relationship between initial concentration of propisochlor and its photodegradation rate was negatively correlated. The changes in acidity and alkalinity of the reaction medium influenced the photoreaction rate evidently. In the alkaline solution the degradation was accelerated. In the reaction media with different pH values, the photolysis followed the first-order kinetics. The presence of dissolved oxygen may promote the photolysis and there existed an optimum of dissolved oxygen concentrations. Increasing the DO level can weaken the promotion and even have an adverse effect. It was demonstrated that with dissolved oxygen the photodegradation of propisochlor followed the first-order kinetics equation. The addition of salt ions Ca2+ and Mg2+ changed the ionic strength and solvent polarity, resulting in the effect on propisochlor photolysis. The photoproducts were detected by both HPLC and GC-MS methods. It was found that photolysis products varied under different light sources. Conclusions may be reached that in the photodegradation of propisochlor, the benzene ring remained intact under irradiation of both solar light and high-pressure mercury lamp, and the amido link was relatively stable, while dechlorination was liable to take place; moreover, alpha-hydrogen at the substituent of benzene ring was active.     

Photodegradation of naproxen in water under simulated solar radiation: mechanism,kinetics, and toxicity variation

The main objective of this study was to investigate the degradation mechanism, the reaction kinetics, and the evolution of toxicity of naproxen in waters under simulated solar radiation. These criteria were investigated by conducting quenching experiments with reactive oxygen species (ROS), oxygen concentration experiments, and toxicity evaluations with Vibrio fischeri bacteria. The results indicated that the degradation of naproxen proceeds via pseudo first-order kinetics in all cases and that photodegradation included degradation by direct photolysis and by self-sensitization via ROS; the contribution rates of self-sensitized photodegradation were 1.4 %, 65.8 %, and 31.7 % via ·OH, ¹O₂ and O₂ ^??, respectively. Furthermore, the oxygen concentration experiments indicated that dissolved oxygen inhibited the direct photodegradation of naproxen, and the higher the oxygen content, the more pronounced the inhibitory effect. The toxicity evaluation illustrated that some of the intermediate products formed were more toxic than naproxen.     

Studies on degradation of glyphosate by several oxidative chemical processes: Ozonation,photolysis and heterogeneous photocatalysis

Several different Advanced Oxidation Processes (AOPs) including ozonation at pH 6.5 and 10, photolysis and heterogeneous photocatalysis using TiO₂ as semiconductor and dissolved oxygen as electron acceptor were applied to study the degradation of glyphosate (N-phosphonomethyl glycine) in water. The degree of glyphosate degradation, the reactions kinetic and the formation of the major metabolite, aminomethyl phosphonic acid (AMPA), were evaluated. Ozonation at pH 10 resulted in the maximum mineralization of glyphosate. It was observed that under the experimental conditions used in this study the degradation of glyphosate followed the first-order kinetics. The half-life obtained for glyphosate degradation in the O₃/pH 10 process was 1.8 minutes.     

Quantitation of Hydroxyl Radicals from Photolysis of Fe(III)-Citrate Complexes in Aerobic Water (5 pp)

Background For their high photoreactivity, Fe(III)-carboxylate complexes are important sources of H2O2 for some atmospheric and surface waters. Citrate is one kind of carboxylate, which can form complexes with Fe(III). In our previous study, we have applied Fe(III)-citrate complexes to degrade and decolorize dyes in aqueous solutions both under UV light and sunlight. Results have shown that carboxylic acids can promote the photodegradation efficiency. It is indicated that the photolysis of Fe(III)-citrate complexes may cause the formation of some reactive species (e. g. H2O2 and ·OH). This work is attempted to quantify hydroxyl radicals generated in the aqueous solution containing Fe(III)-citrate complexes and to interpret the photoreactivity of Fe(III)-citrate complexes for degrading organic compounds. Methods By using benzene as the scavenger to produce phenol, the photogeneration of ·OH in the aqueous solution containing Fe (III)-citrate complexes was determined by HPLC. Results and Discussion In the aqueous solution containing 60.0/30.0 mM Fe(III)/citrate and 7.0 mM benzene at pH 3.0, 96.66 mM ·OH was produced after irradiation by a 250W metal halide light (l ≥ 313 nm) for 160 minutes. Effects of initial pH value and concentrations of Fe(III) and citrate on ·OH radical generation were all examined. The results show that the greatest photoproduction of ·OH in the aqueous solution (pH ranged from 3.0 to 7.0) was at pH 3.0. The photoproduction of ·OH increased with increasing Fe(III) or citrate concentrations. Conclusion In the aqueous solutions containing Fe(III)-citrate complexes, ·OH radicals were produced after irradiation by a 250W metal halide light. It can be concluded that Fe(III)-citrate complexes are important sources of ·OH radicals for some atmospheric and surface waters. Recommendations and Outlook It is believed that the photolysis of Fe(III)-citrate complexes in the presence of oxygen play an important role in producing ·OH both in atmospheric waters and surface water where high concentrations of ferric ions and citrate ions exist. The photoproduction of ·OH has a high oxidizing potential for the degradation of a wide variety of natural and anthropogenic organic and inorganic substances. We can use this method for toxic organic pollutants such as organic dyes and pesticides.     

Effect of humic acids on photodegradation of chloroacetanilide herbicides under UV irradiation

The effects of two humic acids (HAs) of different origins on the photodegradation of the chloroacetanilide herbicides acetochlor, propisochlor and butachlor were investigated in this study. One of the tested HAs was a standard sample that was purchased from a commercial source, and the other was isolated from the black soil of Northeast China. The photolysis of all three herbicides followed pseudo-first-order kinetics under ultraviolet (UV) irradiation conditions, regardless of whether HAs were present or not. Both HAs improved the photolysis rates of acetochlor in a dose-reversed way, whereas they inhibited butachlor degradation under all experimental concentrations. The two HAs differed in their effects on propisochlor photolysis, changing from enhancement to inhibition, depending on the origin and concentration of HAs. Element and Fourier Transform Infrared spectroscopy analyses showed that the isolated HAs had more polysaccharides and less aliphatic groups than the commercial HAs, and it was indicated that some characteristic radicals (C═O, O─H and phenolic hydroxyls) in HAs were involved in the photolysis of the herbicides. Gas chromatography/mass spectrometry (GC/MS) analyses indicated that the presence of HAs had no effects on the photolysis pathway and photoproduct species of the three herbicides.     

Effect of humic acids on photodegradation of chloroacetanilide herbicides under UV irradiation

The effects of two humic acids (HAs) of different origins on the photodegradation of the chloroacetanilide herbicides acetochlor, propisochlor and butachlor were investigated in this study. One of the tested HAs was a standard sample that was purchased from a commercial source, and the other was isolated from the black soil of Northeast China. The photolysis of all three herbicides followed pseudo-first-order kinetics under ultraviolet (UV) irradiation conditions, regardless of whether HAs were present or not. Both HAs improved the photolysis rates of acetochlor in a dose-reversed way, whereas they inhibited butachlor degradation under all experimental concentrations. The two HAs differed in their effects on propisochlor photolysis, changing from enhancement to inhibition, depending on the origin and concentration of HAs. Element and Fourier Transform Infrared spectroscopy analyses showed that the isolated HAs had more polysaccharides and less aliphatic groups than the commercial HAs, and it was indicated that some characteristic radicals (C=O, O-H and phenolic hydroxyls) in HAs were involved in the photolysis of the herbicides. Gas chromatography/mass spectrometry (GC/MS) analyses indicated that the presence of HAs had no effects on the photolysis pathway and photoproduct species of the three herbicides.     

Photodegradation of sulfonamide antibiotics in simulated and natural sunlight: Implications for their environmental fate

The photochemical fate of seven sulfonamides was investigated in matrices representative of natural water bodies under various light sources. Fundamental photolysis parameters such as molar absorption coefficient, quantum yield (QY) and first-order rate constants were determined. The photolysis decay rate was dependent on the protonation state of the molecule, pH of the water sample and dissolved organic matter. Natural organic matter was the most significant factor in the indirect photolysis of sulfonamides. Half-lives were in the range of minutes at 254 nm to days under natural sunlight. Under natural sunlight, all sulfonamides showed higher removal rates in natural waters implying that indirect photolysis is the predominant mechanism.     

硝酸根紫外光降解对硝基苯甲酸的研究

以硝酸铝做光氧化剂,研究了紫外光照射下,NO-3对PNB(对硝基苯甲酸)的光降解作用.探索了NO-3投加量、模拟废水初始浓度和pH值、光照时间、溶解氧浓度对处理效果的影响.结果表明,NO-3对PNB具有良好的光氧化作用,在最佳处理条件下,NO-3光降解PNB 4 h后降解率达90.8%.廉价硝酸盐对于有机物能起到显著光...     

Photolysis of nonylphenol ethoxylates: the determination of the degradation kinetics and the intermediate products

The photolysis of nonylphenol ethoxylates with an average oligomers length of ten ethoxylate units (NPEO(10)) in aqueous solution under UV, as well as the influence of humic acid (HA) on the photolysis was studied. A 125W high-pressure mercury lamp was employed as the light source. The intermediate products from the photolysis were determined by LC-MS. The results indicated that NPEO(10) underwent direct photolysis upon exposed to UV. The degradation pathway was complex. Besides the generally proposed degradation pathway of ethylene oxide (EO) side chains shortening, the oxidation of alkyl chain and EO chain led to intermediates having both a carboxylated (as well as carbonylated) ethoxylate and alkyl chain of varying lengths. The hydrogenation of benzene ring was also detected. The kinetics data showed that the first order reaction kinetics could be well used to describe the kinetics of NPEO(10) degradation. In the presence of dissolved organic matter by HA addition, the performance of NPEO(10) photodegradation was reduced. The photolysis rate decreased with increased HA concentration.     

Nitrate-induced photodegradation of atenolol in aqueous solution: kinetics, toxicity and degradation pathways

The extensive utilization of β-blockers worldwide led to frequent detection in natural water. In this study the photolysis behavior of atenolol (ATL) and toxicity of its photodegradation products were investigated in the presence of nitrate ions. The results showed that ATL photodegradation followed pseudo-first-order kinetics upon simulated solar irradiation. The photodegradation was found to be dependent on nitrate concentration and increasing the nitrate from 0.5 mM L⁻¹ to 10 mM L⁻¹ led to the enhancement of rate constant from 0.00101 min⁻¹ to 0.00716 min⁻¹. Hydroxyl radical was determined to play a key role in the photolysis process by using isopropanol as molecular probe. Increasing the solution pH from 4.8 to 10.4, the photodegradation rate slightly decreased from 0.00246 min⁻¹ to 0.00195 min⁻¹, probably due to pH-dependent effect of nitrate-induced OH formation. Bicarbonate decreased the photodegradation of ATL in the presence of nitrate ions mainly through pH effect, while humic substance inhibited the photodegradation via both attenuating light and competing radicals. Upon irradiation for 240 min, only 10% reduction of total organic carbon (TOC) can be achieved in spite of 72% transformation rate of ATL, implying a majority of ATL transformed into intermediate products rather than complete mineralization. The main photoproducts of ATL were identified by using solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC-MS) techniques and possible nitrate-induced photodegradation pathways were proposed. The toxicity of the phototransformation products was evaluated using aquatic species Daphnia magna, and the results revealed that photodegradation was an effective mechanism for ATL toxicity reduction in natural waters.     

Photodegradation of the antimicrobial triclocarban in aqueous systems under ultraviolet radiation

This work aimed to investigate the effectiveness of ultraviolet (UV) radiation on the degradation of the antimicrobial triclocarban (TCC). We investigated the effects of several operational parameters, including solution pH, initial TCC concentration, photocatalyst TiO₂ loading, presence of natural organic matter, and most common anions in surface waters (e.g., bicarbonate, nitrate, and sulfate). The results showed that UV radiation was very effective for TCC photodegradation and that the photolysis followed pseudo-first-order kinetics. The TCC photolysis rate was pH dependent and favored at high pH. A higher TCC photolysis rate was observed by direct photolysis than TiO₂ photocatalysis. The presence of the inorganic ions bicarbonate, nitrate, and sulfate hindered TCC photolysis. Negative effects on TCC photolysis were also observed by the addition of humic acid due to competitive UV absorbance. The main degradation products of TCC were tentatively identified by gas chromatograph with mass spectrometer, and a possible degradation pathway of TCC was also proposed.     

Hydrolysis and photolysis of oxytetracycline in aqueous solution

Oxytetracycline ((2Z,4S,4aR,5S,5aR,6S,12aS)-2-(amino-hydroxy-methylidene)-4-dimethylamino-5,6,10,11,12a-pentahydroxy-6-methyl-4,4a,5,5a-tetrahydrotetracene-1,3,12-trione) is a member of tetracycline antibiotics family and is widely administered to farm animals for the purpose of therapeutical treatment and health protection. Increasing attention has been paid to the environmental fate of oxytetracycline and other veterinary antibiotics with the occurrence of these antibiotics in the environment. The hydrolysis and photolysis degradation of oxytetracycline was investigated in this study. Oxytetracycline hydrolysis was found to obey the first-order model and similar rate constant values ranging from 0.094 ± 0.001 to 0.106 ± 0.003 day^{? 1} were obtained at different initial concentration ranging from 10 to 230 μ M. Solution pH and temperature were shown to have remarked effects on oxytetracycline hydrolysis. The hydrolysis in pH neutral solution appeared to be much faster than in both acidic and alkaline solutions. Oxytetracycline half-life decreased from 1.2 × 10² to 0.15 day with the increasing temperature from 4 ± 0.8 to 60 ± 1°C. The presence of Ca^{2 +} made oxytetracycline hydrolytic degradation kinetics deviate from the simple first-order model to the availability-adjusted first-order model and greatly slowed down the hydrolysis. Oxytetracycline photolysis was found to be very fast with a degradation rate constant at 3.61 ± 0.06 day^{? 1}, which is comparable to that of hydrolysis at 60°C. The presence of Ca^{2 +} accelerated oxytetracycline photolysis, implying that oxytetracycline become more vulnerable to sunlight irradiation after chelating with Ca^{2 +}. The photolysis may be the dominant degradation pathway of oxytetracycline in shallow transparent water environment.     

Heterogeneous photocatalytic decomposition of benzene on lanthanum-doped TiO2 film at ambient temperature

Lanthanum-doped anatase TiO₂ thin films on glass prepared via a sol–gel process have been shown to have much higher photocatalytic activity for the degradation of gaseous benzene than pure anatase TiO₂ thin film. The photodecomposition of benzene on both types of TiO₂ films follows the first-order kinetics while the CO₂ and CO formation followed the zero-order kinetics. GC/MS identification of the intermediates produced during the photodegradation of benzene revealed that doping lanthanum into TiO₂ thin film favors a cleavage of benzene ring. An optimal lanthanum amount with respect to photocatalytic activity was about 2.5 wt% (La₂O₃/TiO₂).     

光源和溶剂对十溴联苯醚光降解的影响

研究了不同光源和溶剂对十溴联苯醚(DecaBDE)光降解特性的影响,并对其降解产物进行了探讨.结果表明,在所试光源和溶剂条件下,DecaBDE均有一定程度的光降解,且都近似符合一级降解动力学.同一光源下,不同溶剂对DecaBDE降解表现出不同的影响.在太阳光照射下,DecaBDE降解速率为甲苯>甲醇>正己烷>正己烷/丙酮>甲醇/水>乙醇/水;在模拟光源照射下,DecaBDE降解速率为甲苯>甲醇>甲醇/水>乙醇/水>正己烷>正己烷/丙酮;在紫外光照射下,DecaBDE降解速率为甲苯>甲醇>正己烷/丙酮>正己烷>甲醇/水>乙醇/水.同一溶剂中,DecaBDE降解速率均为紫外光>太阳光>模拟光源.尽管光源和溶剂对DecaBDE降解速率产生了一定影响,但降解途径基本一致,均为DecaBDE经光解脱溴产生低溴联苯醚.     

Photodegradation of azithromycin in various aqueous systems under simulated and natural solar radiation: kinetics and identification of photoproducts

This article describes the photolysis of azithromycin, a macrolide antibiotic with reported occurrence in environmental waters, under simulated solar radiation. The photodegradation followed first-order reaction kinetics in five matrices examined. In HPLC water, the degradation rate was the slowest (half-life: 20 h), whereas in artificial freshwater supplemented with nitrate (5 mg L⁻¹) or humic acids (0.5 mg L⁻¹) the degradation of azithromycin was enhanced by factors of 5 and 16, respectively, which indicated the role of indirect photolysis involving the formation of highly reactive species. Following chromatographic separation on a UPLC system, the characterization of the transformation products was accomplished using high-resolution QqToF-MS analysis. The presence of seven photoproducts was observed and their formation was postulated to originate from (bis)-N-demethylation in the desosamine sugar, O-demethylation in the cladinose sugar, combinations thereof, as well as from hydrolytic cleavages of the desosamine and/or cladinose residue. Two of these photoproducts could also be detected in natural photodegradation process in river water which was spiked with azithromycin.     

Photochemical behaviour of carbendazim in aqueous solution

To elucidate the photochemical behaviour of carbendazim (or MBC) in superficial waters, photolysis studies have been carried out in aqueous solutions at several pH using a UV light source (high pressure mercury arc lamp) or a solar light simulator (xenon arc lamp). The kinetics of photodecomposition of carbendazim was determined using HPLC-DAD and the identification of photoproducts was carried out with HPLC-MS (ESI negative and positive mode). According to the experimental results carbendazim is a rather stable molecule in the dark or in environmental conditions. The pH influence of the environmental medium on the photodegradation rate has been confirmed. The photochemical process can be considerably accelerated in alkaline solutions using HPK-quartz irradiation (quantum efficiency at pH 9 phi = 3.1 x 10(-3) degraded molecule per absorbed photon) while the photodegradation is not as efficient under a simulated sun irradiation (quantum efficiency in the suntest phi = 10(-4) at pH 7). Three photoproducts have been tentatively identified in pure water: 2-aminobenzimidazole, benzimidazole isocyanate and monocarbomethoxy-guanidine (issued from the cleavage of the benzimidazole ring). The last one seems very stable and could be accumulated in the environment.     

Photodegradation of the novel fungicide fluopyram in aqueous solution: kinetics,transformation products,and toxicity evolvement

The aqueous photodegradation of fluopyram was investigated under UV light (λ?≥?200 nm) and simulated sunlight irradiation (λ?≥?290 nm). The effect of solution pH, fulvic acids (FA), nitrate (NO₃ ^?), Fe (III) ions, and titanium dioxide (TiO₂) on direct photolysis of fluopyram was explored. The results showed that fluopyram photodegradation was faster in neutral solution than that in acidic and alkaline solutions. The presence of FA, NO₃ ^?, Fe (III), and TiO₂ slightly affected the photodegradation of fluopyram under UV irradiation, whereas the photodegradation rates of fluopyram with 5 mg L^?1 Fe (III) and 500 mg L^?1 TiO₂ were about 7-fold and 13-fold faster than that without Fe (III) and TiO₂ under simulated sunlight irradiation, respectively. Three typical products for direct photolysis of fluopyram have been isolated and characterized by liquid chromatography tandem mass spectrometry. These products resulted from the intramolecular elimination of HCl, hydroxyl-substitution, and hydrogen extraction. Based on the identified transformation products and evolution profile, a plausible degradation pathway for the direct photolysis of fluopyram in aqueous solution was proposed. In addition, acute toxicity assays using the Vibrio fischeri bacteria test indicated that the transformation products were more toxic than the parent compound.     

Photocatalytic Degradation of an Organophosphorus Pesticide Phosalone in Aqueous Suspensions of Titanium Dioxide

Abstract

The present work deals with photocatalytic degradation of an organophosphorus pesticide, phosalone, in water in the presence of TiO₂ particles under UV light illumination (1000 W). The influence of the basic photocatalytic parameters such as pH of the solution, amount of TiO₂, irradiation time, stirring rate, and distance from UV source, on the photodegradation efficiency of phosalone was investigated. The degradation rate of phosalone was not high when the photolysis was carried out in the absence of TiO₂ and it was negligible in the absence of UV light. The half-life (DT₅₀) of a 20 ppm aqueous solution of phosalone was 15 min in optimized conditions. The plot of lnC (phosalone) vs. time was linear, suggesting first order reaction (K = 0.0532 min^?1). The half-life time of photomineralization in the concentration range of 7.5–20 ppm was 13.02 min. The efficiency of the method was also determined by measuring the reduction of Chemical Oxygen Demand (COD). During the mineralization under optimized conditions, COD decreased by more than 45% at irradiation time of 15 min. The photodegradation of phosalone was enhanced by addition of proper amount of hydrogen peroxide (150 ppm).     

活性污泥硝化过程的动态响应信号

把pH值在线监测与药品自动投加系统与已开发的混合呼吸测量仪集成,组成自动呼吸-滴定测量仪,同时测得废水生物处理过程溶解氧（DO）、pH、氧气利用速率（OUR）和质子变化速率（HVR）。分别监测了只投加NH4＋-N底物的活性污泥硝化过程和实验室脱氮除碳SBR曝气阶段的DO/pH响应,结果显示,两信号呈一定规律变化,在反应...     

Aerobic sludge digestion under low dissolved oxygen concentrations.

Low dissolved oxygen (DO) concentrations occur commonly in aerobic digesters treating thickened sludge, with benefits of smaller digester size, much reduced aeration cost, and higher digestion temperature (especially important for plants in colder areas). The effects of low DO concentrations on digestion kinetics were studied using the sludge from municipal wastewater treatment plants in Akron, Ohio, and Los Lunas, New Mexico. The experiments were conducted in both batch digestion and a mixed mode of continuous, fed-batch, and batch operations. The low DO condition was clearly advantageous in eliminating the need for pH control because of the simultaneous occurrence of nitrification and denitrification. However, when compared with fully aerobic (high DO) systems under constant pH control (rare in full-scale plants), low DO concentrations and a higher solids loading had a negative effect on the specific volatile solids (VS) digestion kinetics. Nonetheless, the overall (volumetric) digestion performance depends not only on the specific digestion kinetics, but also the solids concentration, pH, and digester temperature. All of the latter factors favor the low DO digestion of thickened sludge. The significant effect of temperature on low DO digestion was confirmed in the mixed-mode study with the Akron sludge. When compared with the well-known empirical correlation between VS reduction and the product (temperature x solids retention time), the experimental data followed the same trend, but were lower than the correlation predictions. The latter was attributed to the lower digestible VS in the Akron sludge, the slower digestion at low DO concentrations, or both. Through model simulation, the first-order decay constant (kd) was estimated as 0.004 h(-1) in the mixed-mode operations, much lower than those (0.011 to 0.029 h(-1)) obtained in batch digestion. The findings suggested that the interactions among sludges with different treatment ages may have a substantially negative effect on digestion kinetics. The use of multistage digesters, especially with small front-end reactors, may be advantageous in both "process" kinetics and "biological reaction" kinetics for sludge digestion.