Effects of fulvic acid concentration and origin on photodegradation of polycyclic aromatic hydrocarbons in aqueous solution: Importance of active oxygen

With an Xe arc lamp house as simulated sunlight, the influences of fulvic acid (FA) concentration and origins on photodegradation of acenaphthene, fluorine, phenanthrene, fluoranthene and pyrene in aqueous solution have been studied. Similar effects of FAs, collected from five places around China, on polycyclic aromatic hydrocarbon (PAH) photodegradation have been observed. Active oxygen was of significance in PAH photodegradation with the presence of FAs. For systems with 1.25 mg L⁻¹ FAs, the contributions of OH to PAH photodegradation rates were from 33% to 69%. FAs had two opposite effects, i.e., stimulating the generation of active oxygen and advancing PAH photodegradation; competing with PAHs for energy and photons and restraining PAH photodegradation. Generally, photodegradation rates of the 5 PAHs decreased with the increase of FAs concentration; except fluoranthene and pyrene were advanced in solutions with low FA concentration. The influences of FA concentration on PAH photodegradation were more significant than FA origin.     

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.     

Degradation of lidocaine,tramadol, venlafaxine and the metabolites O-desmethyltramadol and O-desmethylvenlafaxine in surface waters

The photodegradation and biotic transformation of the pharmaceuticals lidocaine (LDC), tramadol (TRA) and venlafaxine (VEN), and of the metabolites O-desmethyltramadol (ODT) and O-desmethylvenlafaxine (ODV) in the aquatic environmental have been investigated. Photodegradation experiments were carried out using a medium pressure Hg lamp (laboratory experiments) and natural sunlight (field experiments). Degradation of the target compounds followed a first-order kinetic model. Rates of direct photodegradation (light absorption by the compounds itself) at pH 6.9 were very low for all of the target analytes (?0.0059 h^?1 using a Hg lamp and ?0.0027 h^?1 using natural sunlight), while rates of indirect photodegradation (degradation of the compounds through photosensitizers) in river water at pH 7.5 were approximately 59 (LDC), 5 (TRA), 8 (VEN), 15 (ODT) and 13 times (ODV) higher than the rates obtained from the experiments in ultrapure water. The accelerated photodegradation of the target compounds in natural water is attributed mainly to the formation of hydroxyl radicals through photochemical reactions. Biotic (microbial) degradation of the target compounds in surface water has been shown to occur at very low rates (?0.00029 h^?1). The half-life times determined from the field experiments were 31 (LDC), 73 (TRA), 51 (VEN), 21 (ODT) and 18 h (ODV) considering all possible mechanisms of degradation for the target compounds in river water (direct photodegradation, indirect photodegradation and biotic degradation).     

A novel BiVO4-GO-TiO2-PANI composite for upgraded photocatalytic performance under visible light and its non-toxicity

A novel non-toxic hybrid BiVO₄-GO-TiO₂-polyaniline (PANI) (BVGT-PANI) composite with superior photocatalysis was successfully prepared via a one-pot hydrothermal reaction. The structural and morphological characterizations of the synthesized compounds were analyzed by a series of techniques. We found excellent photocatalytic efficiencies for methylene blue (MB) and phenol degradation under visible light irradiation after adhering the PANI to the photocatalyst. The degradation rates of MB and phenol reach up to approximately 85% and 80%, respectively, after 3 h of irradiation. For photodegradation MB, BVGTA exhibit the highest k_app rate constant of about 1.06?×?10^?2 min^?1, which is about 1.63-fold faster than BVG and 2.94-fold faster than BVGT. For photodegradation of phenol, BVGTA exhibits the highest k_app rate constant, of about 8.86?×?10^?3min^?1, which is about 1.2-fold faster than BVG and 1.96-fold faster than BVGT. Furthermore, vitro toxicity test against Bacillus subtilis and Staphylococcus aureus demonstrated that the nanophotocatalyst is non-toxic.

     

Degradation of polychlorinated dibenzo-p-dioxins in aqueous solution by Fe(II)/H2O2/UV system

The photodegradation of polychlorinated dibenzo-p-dioxins (PCDDs), which include tetra- to octa-CDDs (TeCDD, PeCDD, HxCDD, HpCDD and OCDD), was carried out in the presence of Fe(II) and H2O2 mixed reagent. The degradation efficiency was strongly influenced by UV irradiation, and the initial concentrations of H2O2 and Fe(II). An initial TeCDD concentration of 10 ng l(-1) was completely degraded within 20 min under the optimum conditions. All PCDDs tested were successfully degraded by Fe(II)/H2O2/UV treatment and complete degradation of TeCDD, PeCDD and HxCDD was achieved within 120 min. PCDD photodegradation rates decreased with the number of chlorine atoms. The degradation process of TeCDD by this system seems to be initiated by an oxidative reaction (OH* radical attack) because less chlorinated DDs as intermediate products were not detected. From the Frontier electron density calculation, the first OH* radical attack positions on TeCDD were found to be four C atoms neighboring two O atoms. The decomposition of TeCDD gave 4,5-dichlorocatechol as an intermediate product. A TeCDD degradation scheme was proposed based on the identified intermediate and the values of Frontier electron density. Based on these results, Fe(II)/H2O2/UV system could be useful technology for the treatment of wastewater containing persistent pollutants such as dioxins and polychlorinated biphenyls.     

Photocatalytic decomposition of crotamiton over aqueous TiO(2) suspensions: determination of intermediates and the reaction pathway

The photocatalytic degradation of crotamiton in aqueous solution using TiO₂ was investigated. To investigate the effect of initial pH, the photodegradation behaviors of three types of pharmaceuticals were compared (crotamiton, clofibric acid, sulfamethoxazole). The degradation rates of crotamiton in the pH range 3-9 were nearly equal, but those of clofibric acid and sulfamethoxazole were affected by pH. At pH > 6.5, TiO₂ particles, clofibric acid and sulfamethoxazole had negative charge, therefore, the repulsive force between TiO₂ particles and anionic pharmaceuticals occurred and a low reaction rate at high pH was observed. The effect of UV intensity and TiO₂ concentration on photodegradation efficiency was also investigated. Linear and logarithmical relationships between UV intensity, TiO₂ concentration and the reaction rate constant were confirmed. Furthermore, the structures of photodegradation intermediates formed concomitantly with the disappearance of crotamiton were estimated. Seven intermediates were characterized by LC/MS/MS analyses, and it was assumed that the photocatalytic degradation of crotamiton was initiated by the attack of electrophilic hydroxyl radicals on aromatic rings and alkyl chains.     

水中四环素类化合物在不同光源下的光降解

研究了模拟太阳光和实际室外太阳光下四环素类化合物在水溶液中的光降解。结果表明,四环素类化合物(TCs)在模拟太阳光照射下均能发生直接光降解,且其降解速率随pH不同变化很大。四环素(TC)、土霉素(OTC)、金霉素(CTC)和多西环素(DTC)的光降解速率随溶液pH升高明显加快,而米诺环素(MTC)在水中的光降解速率随溶液pH升高略有下降。天然水体pH范围内,模拟太阳光照下四环素类化合物表观光降解速率常数在0.004～0.026 min-1范围内,降解半衰期在26～136 min范围内。在室外实际太阳光照下,四环素类化合物光降解反应速率与太阳光强成正比例关系。晴朗无云天气下,四环素类化合物降解半衰期在春冬季节较长、夏季节较短;四环素在东江实际水体中表观光降解速率很快,在冬季晴天天气下,其平均半衰期仅为8.2 min。     

The modelling of trichloroethene photodegradation in Brij 35 surfactant by two-stage reaction.

Various clean-up technologies have been developed for the removal and/or destruction of trichloroethene (TCE) in the subsurface. Surfactant-aided soil washing followed by photodegradation could be a promising approach to such a task. The modelling of TCE photodegradation by UV in Brij 35 surfactant micelles is therefore investigated. Two stages of TCE degradation are observed in surfactant Brij 35 systems. A lag phase is observed at the commencement of the degradation, but the duration of the lag phase is significantly reduced as the initial pH increases. As the overall decay of TCE is also found to be faster at higher pH levels, it is suggested that the free radical reaction is dominant at high pH levels, and the formation of lag phases is mainly due to the deficiency of free radicals at lower pH levels. Since the period of the lag phase gradually decreases with the increase of initial pH level, and the two pseudo first-order reaction constants (one for the lag phase and one for the subsequent fast decay) for TCE decay in both stages are also pH dependent, a non-steady-state mathematical model is developed for the prediction of TCE photodegradation in Brij 35 solutions, in which the remaining fraction of TCE (C/C0) in the system can be determined at any instant by using a simple parameter of the initial system pH.     

The study of lag phase and rate improvement of TCE decay in UV/surfactant systems

The photodegradation of trichloroethene (TCE) in surfactant micelles was investigated. The decay of TCE was studied in the Rayonet RPR-200 merry-go-round photoreactor, at 253.7 nm monochromatic ultraviolet (UV) lamps, in the presence of surfactants. Surfactants are used as additional hydrogen sources to improve the photodegradation rates of TCE. About three times the rate increment is observed in the presence of Brij 35 surfactant micelles than in water alone. The increasing concentrations of H+ and Cl- indicate that they are the final products of TCE photodegradation (i.e. photodechlorination is the dominant mechanism in this system). A lag phase is observed at the beginning of the degradation, but the duration of the lag phase is apparently reduced as the initial pH increases. Because the overall decay of TCE is also found faster at higher pH levels, it is suggested that the free radical reaction is dominant at high pH levels, and the formation of lag phases is mainly due to the deficiency of free radicals at lower pH levels. The photodecomposition of TCE in surfactant micelles is also proven to be a clean and effective process. It generates no chlorinated by-products or intermediates during the process, and TCE is fully decomposed within a reasonable time.     

Photodegradation and volatility of pesticides

BACKGROUND AND OBJECTIVES: Among the factors affecting the environmental fate of surface-applied pesticides several biological as well as abiotic factors, such as volatilization and photochemical transformations are of particular interest. Whereas reliable measurement methods and models for estimating direct photodegradation are already available for the compartments of water and atmosphere and individual subprocesses have already been described in detail, there is still a need for further elucidation concerning the key processes of heterogeneous photodegradation of environmental chemicals on surfaces. METHODS: In order to systematically examine the direct and indirect photodegradation of 14C-labeled pesticides on various surfaces and their volatilization behavior, a new laboratory device ('photovolatility chamber') was designed according to US EPA Guideline 161-3. Model experiments under controlled conditions were conducted investigating the impact of different surfaces, i.e. glass, soil dust and radish plants, and environmental factors, i.e. irradiation and atmospheric ozone (O3), on the photodegradation and volatilization of surface-deposited [phenyl-UL-14C]parathion-methyl (PM). RESULTS AND DISCUSSION: Depending on the experimental conditions, parathion-methyl was converted to paraoxon-methyl, 4-nitrophenol, unknown polar products and 14CO2. With respect to the direct photodegradation of PM (experiments without O3), the major products were polar compounds and 14CO2, due to the rapid photochemical mineralization of 4-nitrophenol to 14CO2. Paraoxon-methyl and 4-nitrophenol formation was mainly mediated by the combination of light, O3, and *OH radicals. In radish experiments PM photodegradation was presumably located in the cuticle compartment, which exhibited a sensitized photodegradation, as more unknown products were yielded compared to the glass and soil dust experiments. This could be explained by intensifying the inherent PM degradation in the dark with the same product spectrum. Due to photochemical product formation, which is an antagonistic process to the volatilization of parent compound, the volatilization of unaltered parathion-methyl from each surface generally decreased in the presence of light, particularly in combination with increasing O3 concentrations and *OH radical production rates. CONCLUSION: First results demonstrated that the photovolatility chamber provides a special tool for the systematic evaluation of (a) photodegradation of surface-located pesticide residues, i.e. measuring qualitative aspects of direct and indirect photodegradation together with relative photodegradation rates, and (b) volatilization of pesticides on surfaces by including and optionally varying relevant parameters such as light, atmospheric O3 concentration, surface temperature, air temperature, air flow rate. OUTLOOK: The experimental facility represents an important complement to lysimeter and field studies, in particular for experiments on the volatilization of pesticides using the wind tunnel system. With the photovolatility chamber special experiments on photodegradation, volatilization and plant uptake can be conducted to study key processes in more detail and this will lead to a better understanding of the effects of certain environmental processes on the fate of released agrochemicals contributing to an improved risk assessment.     

Photochemical behavior of fenpropathrin and λ-cyhalothrin in solution

The photodegradation processes of fenpropathrin and λ-cyhalothrin were studied in hexane, methanol/water (1:1, v/v), and acetone in both ultraviolet light and simulated sunlight. Intermediates in the photodegradation process were identified using gas chromatography/mass spectrometry (GC/MS), and the analysis of intermediates was used to speculate on possible photodegradation pathways. The photodegradation processes of fenpropathrin and λ-cyhalothrin followed pseudo first-order kinetics. The photodegradation rates varied according to the solvent in decreasing order: hexane?>?methanol/water (1:1, v/v)?>?acetone. The effects of substances coexisting in the environment on the photodegradation of pyrethroids were also investigated in the research. Acetone, humic acid, and riboflavin increased photodegradation rates while l-ascorbic acid slowed the process. This study provides a theoretical basis for the removal of pyrethroid pollution from the natural environment.     

Trichloroethylene degradation by photocatalysis in annular flow and annulus fluidized bed photoreactors

The effects of trichloroethylene (TCE) gas flow rate, relative humidity, TiO(2) film thickness, and UV light intensity on photodegradation of TCE have been determined in an annular flow type photoreactor. Phosgene and dichloroacetyl chloride formation could be controlled as a function of TCE gas flow rate and photodegradation of TCE decreased with increasing relative humidity. The optimum thickness of TiO(2) film was found to be approximately 5 mum and the photocatalytic reaction rate of TCE increased with square root of UV light intensity. In addition, the effects of the initial TCE concentration, phase holdup ratio of gas and solid phases (epsilon(g)/epsilon(s)), CuO loading on the photodegradation of TCE have been determined in an annulus fluidized bed photoreactor. The TCE photodegradation decreased with increasing the initial TCE concentration. The optimum conditions of the phase holdup ratio (epsilon(g)/epsilon(s)) and CuO wt.% for the maximum photodegradation of TCE was found to be 2.1 and 1.1 wt.%, respectively. Therefore, an annulus fluidized bed photoreactor is an effective tool for TCE degradation over TiO(2)/silica gel with efficient utilization of photon energy.     

Highly concentrated phenolic wastewater treatment by the photo-Fenton reaction, mechanism study by FTIR-ATR

Phenol degradation by Photo-Fenton reaction has been studied in highly concentrated wastewaters and most intermediate species have been identified by Fourier Transform IR-Spectroscopy with ATR device. During the photodegradation of highly concentrated phenol solutions, the formation of dissolved and precipitate tannin has been observed. The possibility of a Fe3+-Pyrogallol complex formation, previous to the tannin formation, has been proposed too. The complex formation involving Fe3+ ions could be related to the observed Photo-Fenton activity decrease. Tannin formation inhibits the complete mineralization of phenol because *OH radicals attack will produce further condensation steps and the polymer size increase. This fact limits the applicability of the process for highly concentrated phenolic wastes mineralization. However, the tannin precipitation allows its separation from the solution by conventional filtration, and reduction of the corresponding dissolved organic carbon. These observations have been proved from the identification of primary degradation products, catechol and hydroquinone. Catechol is considered to be the first step for the formation of tannins. Degradation process for phenol, catechol and hydroquinone have been monitored by total organic carbon (TOC) measurements along the reaction time span. From these results, a global mechanism for the Photo-Fenton degradation of phenol is proposed.     

Photodegradation of ethylenediaminetetraacetic acid (EDTA) and ethylenediamine disuccinic acid (EDDS) within natural UV radiation range.

The rate of photodegradation of two chelating agents, ethylenediaminetetraacetic acid (EDTA) and an isomeric mixture of ethylenediamine disuccinic acid (EDDS), was analysed in humic lake water and in distilled water using exposure to sunlight, and in the laboratory using lamps emitting UV radiation in the range 315-400 nm. Degradation was studied using Fe(III) complexes and sodium salts of chelates. Fe(III) complexes were illuminated at pH 3.1 and 6.5. The results demonstrated that the rate of photodegradation of Fe(III)-EDTA and Fe(III)-EDDS complexes seems to be pH dependent. In the laboratory experiments degradation occurred much faster when the original pH was 3.1 rather than 6.5. The photodegradation of the isomeric mixture of EDDS was markedly faster than the degradation of EDTA both in the laboratory and field experiments, and both in humic and distilled water. The results indicated that in natural waters photodegradation of EDDS is independent of initial speciation of EDDS, while degradation of EDTA is dependent on its existence as Fe(III)-EDTA species.     

Polychlorinated dibenzothiophenes in Japanese environmental samples and their photodegradability and dioxin-like endocrine-disruption potential

Polychlorinated dibenzothiophenes (PCDTs) in sediment, soil, and fly ash samples collected in Japan were analyzed and their dioxin-like endocrine-disruption potential and photodegradability investigated. PCDTs were detected in all three types of sample, although the concentrations were lower than those of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). An Ah-immunoassay confirmed that 2,3,7,8-TeCDT, 1,2,3,7,8-PeCDT, 1,2,3,7,8,9-HxCDT, and 1,2,3,4,7,8,9-HpCDT had Ah receptor-binding activities, which means that these PCDTs have the potential to cause dioxin-like endocrine-disruption. Photodegradation of PCDTs by UV irradiation was accompanied by dechlorination. The photodegradation rates of 2,3,7,8-TeCDT and OCDT were lower than the rates for the corresponding PCDF isomers (2,3,7,8-TeCDF and OCDF), which indicates that PCDTs are more stable than PCDFs to photodegradation.     

New TiO2/C sol-gel electrodes for photoelectrocatalytic degradation of sodium oxalate

This paper reports the preparation of carbon doped TiO2 electrodes by a modification of a sol-gel route. The electrodes have been characterized by measuring their photocurrent, as a function of applied potential. Their photoelectrocatalytic activity, relative to similar sol-gel electrodes without carbon, has been assessed by measuring the decomposition of a 10 mM sodium oxalate solution. Measurements have been made on electrodes prepared with 2%, 5% and 10% of active carbon. The highest photocurrents and the highest photoelectrocatalytic activity were both obtained with electrodes prepared by heating, at 600 degrees C, electrodes prepared with 5% of active carbon. All the electrodes showed evidence of enhanced photocatalytic activity at 1.2 V. Five percent addition of C double the measured rates of photodegradation, even though, in these preliminary studies, no attempt has been made to optimize the type of carbon or the details of the electrode preparation.     

Evaluation of the Use of Solar Irradiation for the Decontamination of Soils Containing Wood Treating Wastes

Laboratory evaluation of the efficacy of soil phase photodegradation of recalcitrant hazardous organic components of wood treating wastes is described. The photodecomposition of anthracene, biphenyl, 9H-carbazole, m-cresol, dibenzofuran, fluorene, pentachlorophenol, phenanthrene, pyrene and quinoline under UV and visible light was monitored over a 50-day reaction period in three test soils. Methylene blue, riboflavin, hydrogen peroxide, peat moss and diethylamine soil amendments were evaluated as to their effect on the enhancement of compound photoreaction rates in the test soil systems. Dark control samples monitored over the entire study period were utilized to quantify non-photo mediated reaction losses. Compounds losses in both the dark control and irradiated samples were found to follow first order kinetics, allowing the calculation of first order photodegradation reaction rate constants for each test soil/compound combination. Degradation due to photochemical activity was observed for all test compounds, with compound photolytic half-lives ranging from 7 to approximately 180 days. None of the soil amendments were found to improve soil phase photodegradation, although photosensitization by anthracene was shown to significantly enhance the rate of photodegradation of the other test compounds. Soil type, and its characteristic of internal reflectance, proved to be the most significant factor affecting compound degradation rates suggesting the necessity for site specific assessments of soil phase photodegradation potential.     

Dissipation of triadimefon on the solid/gas interface.

The dissipation of triadimefon, as pure solid and in the Bayleton 5 commercial formulation, was studied under controlled and natural conditions. Volatilization and photodegradation were shown to be the main dissipation processes. The volatilization results can be described by an empirical model assuming exponential decay of the volatilization rate. The filler of the commercial formulation is determinant for the volatilization but has little effect on the photodegradation rates. The main photoproducts were identified and a reaction mechanism proposed.     

TiO2光催化降解水中土霉素的动力学研究

环境中抗生素的出现及其引起的危害正受到越来越多的关注。以高压汞灯为光源,选用较为广泛的抗生素土霉素（OTC）为处理对象。考察了初始质量浓度、反应过程中光照、催化剂投加量、溶液起始pH、溶液中DOM和NO^-₃对光催化降解的影响,研究了其光降解动力学。结果表明,TiO₂光催化氧化法能够有效去除水中半微量的OTC,OTC的光降解过程符合一级反应动力学模型;UV/TiO₂联用工艺对TOC也有很好的去除效果,反应90 min,TOC去除率可达74%;OTC的初始浓度从30 mg/L增大到90 mg/L,反应速率从0.0619 min^-1降低到0.0130 min^-1;随着光催化剂投加量的增大,光降解速率常数先增大后减小;增加溶液的pH值,速率常数逐渐减小;溶液中的DOM和NO^-₃也可以影响光降解效率。