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.     

Photodegradation of hexabromocyclododecane (HBCD) by Fe(III) complexes/H2O2 under simulated sunlight

Hexabromocyclododecane (HBCD) is a globally produced brominated flame retardant used primarily as an additive flame retardant in polystyrene and textile products. Photodegradation of HBCD in the presence of Fe(III)-carboxylate complexes/H₂O₂ was investigated under simulated sunlight. The degradation of HBCD decreased with increasing pH in the Fe(III)-oxalate solutions. In contrast, the optimum pH was 5.0 for the Fe(III)-citrate-catalyzed photodegradation within the range of 3.0 to 7.0. For both Fe(III)-oxalate and Fe(III)-citrate complexes, the increase of carboxylate concentrations facilitated the photodegradation. The photochemical removal of HBCD was related to the photoreactivity and speciation distribution of Fe(III) complexes. The addition of H₂O₂ markedly accelerated the degradation of HBCD in the presence of Fe(III)-citrate complexes. The quenching experiments showed that ·OH was responsible for the photodegradation of HBCD in the Fe(III)-carboxylate complexes/H₂O₂ solutions. The results suggest that Fe(III) complexes/H₂O₂ catalysis is a potential method for the removal of HBCD in the aqueous solutions.     

Photodegradation of Dyes in Aqueous Solutions containing Fe(III) -hydroxy Complex II. Solar Photodegradation Kinetics

The solar photodegradation of five dyes, C.I. reactive red 2, C.I. reactive blue 4, C.I. reactive black 8, C.I. basic red 13, and C.I. basic yellow 2, were studied in a sunlight/Fe(III)-hydroxy system. It was observed that the photodegradation of these five dyes were pseudo-first order reactions, which has a little difference with the photodegradation kinetics of the dyes with UV-light as the irradiation source. The comparison between the two studies is also conducted.     

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.     

还原铁粉/紫外光体系对活性艳红X-3B溶液的脱色

研究了在紫外杀菌灯（λmax=253．7nm,30W）照射下,添加还原铁粉的活性艳红X－3B水溶液的脱色作用。当pH=3．5,铁粉投加量为2．0g／L时,20mg／L活性艳红X－3B溶液在光照180min后的脱色率为79％。脱色为动力学零级反应。染料溶液的pH、铁粉投加量、活性艳红初始浓度对脱色有影响。初步探讨了脱色反应的机理。     

Solar light induced and TiO2 assisted degradation of textile dye reactive blue 4

Aqueous solutions of reactive blue 4 textile dye are totally mineralised when irradiated with TiO2 photocatalyst. A solution containing 4 x 10(-4) M dye was completely degraded in 24 h irradiation time. The intensity of the solar light was measured using Lux meter. The results showed that the dye molecules were completely degraded to CO2, SO4(2-), NO3-, NH4+ and H2O under solar irradiation. The addition of hydrogen peroxide and potassium persulphate influenced the photodegradation efficiency. The rapidity of photodegradation of dye intermediates were observed in the presence of hydrogen peroxide than in its absence. The auxiliary chemicals such as sodium carbonate and sodium chloride substantially affected the photodegradation efficiency. High performance liquid chromatography and chemical oxygen demand were used to study the mineralisation and degradation of the dye respectively. It is concluded that solar light induced degradation of textile dye in wastewater is a viable technique for wastewater treatment.     

Photochemistry of hydrolytic iron (III) species and photoinduced degradation of organic compounds. A minireview

On the basis of the research literature of the last fifty years, we have reviewed the photochemical properties of different hydrolytic Fe(III) species and the photodegradation of organic compounds in aqueous solutions initiated by them (mainly including low-molecular-weight Fe(III)-OH complexes, Fe(III) oxides (Fe2O3) and Fe(III) hydroxides (FeOOH)). Furthermore, the feasibility and prospects of the novel photochemical methods of using Fe(III) salts and oxides in wastewater treatments are being discussed in this paper.     

Photoinductive activity of humic acid fractions with the presence of Fe(III): the role of aromaticity and oxygen groups involved in fractions

Relationship between the photoinductive activity and the properties of humic acids (HA) fractions were investigated with and without Fe(III). Three fractions were separated based on the molecular weight (M(w)) and were obtained following the order of M(w): F(A)>F(B)>F(C). Compared to F(A) and F(B), photodegradation of atrazine under simulated sunlight was much faster in solution containing F(C), whose structure was dominated by greater aromaticity, more oxygen groups and fluorophores. The interaction of HA fractions and Fe(III) was studied using fluorescence spectrometry and F(C) had the largest quenching constant. The capacity of electron transfer, estimated from the amount of photoformed Fe(II), was also highest for F(C). Thus, the Fe(III)-F(C) complex was efficient in phototransformation of atrazine in nearly neutral aqueous solutions. These results suggest that the aromaticity and oxygen groups content of HA exert great influence on the binding ability of metals and on the fate of pollutants in natural waters.     

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.     

缺氧-好氧生物滤池中高效菌对活性红KN-3B的降解特性

为了研究高效脱色菌在缺氧好氧生物滤池（A/O biofilter）中对偶氮染料的降解特性，以活性红KN-3B（C.I. reactive red 180）为降解对象，缺氧生物滤池以火山碎石为填料，接种高效脱色菌CK3柯氏柠檬酸杆菌启动，好氧生物滤池以牡蛎壳为填料，接种污水处理厂活性污泥启动。试验考察了不同工况下缺氧-好氧生物滤池对色度和COD的去除效果，结果表明：生物滤池中微生物对偶氮染料活性红KN-3B的脱色和对COD降解的最适pH条件为弱酸性；缺氧滤池中高效菌对色度的去除需要外加碳源，且增加外加碳源有助于脱色率的提高；该高效菌为耐盐菌，当进水NaCl浓度达30 g/L时，色度去除率仍可达93%以上；当染料负荷达500 mg/L时，脱色率仍可达95%。通过紫外-可见扫描图谱分析初步推断CK-3柯氏柠檬酸杆菌对偶氮染料活性红KN-3B的脱色主要是生物降解作用。     

Degradation mechanism of azo dye C. I. reactive red 2 by iron powder reduction and photooxidation in aqueous solutions

We have made a comparison of the UV-VIS spectra of three azo dyes, C. I. reactive red 2, orange II and C. I. reactive black 8, in aqueous solutions during treatment with iron powder reduction and photooxidation. From this, we propose their mechanisms for reduction photooxidation. GC/MS analyses of the degradation products of the dye C. I. reactive red 2 demonstrated some important steps producing hydrogenated azo structure, substituted benzene and substituted naphthalene.     

蒸发壁式超临界水氧化反应器处理分散红和活性红染料废水的比较

采用蒸发壁式超临界水氧化反应器对染料分散红C.I.60和活性艳红M-2B配制的模拟废水进行降解实验.实验结果表明,2种染料的COD和TN去除率随着反应温度、氧化剂过量比(r)的升高而上升.COD去除率活性红要高于分散红,而TN去除率则相反.根据GC-MS分析和陶瓷膜SEM图像,分析测得2种染料主要反应中间产物均含有苯酚和苯甲酸,2种染料的反应对陶瓷膜均有轻微的腐蚀.     

Behavior and mechanism of arsenate adsorption on activated natural siderite: evidences from FTIR and XANES analysis

Activated natural siderite (ANS) was used to investigate its characteristics and mechanisms of As(V) adsorption from aqueous solution. Batch tests were carried out to determine effects of contact time, initial As(V) concentration, temperature, pH, background electrolyte, and coexisting anions on As(V) adsorption. Arsenic(V) adsorption on ANS well-fitted pseudo-second-order kinetics. ANS showed a high-adsorption capacity of 2.19 mg/g estimated from Langmuir isotherm at 25 °C. Thermodynamic studies indicated that As(V) adsorption on ANS was spontaneous, favorable, and endothermic. ANS adsorbed As(V) efficiently in a relatively wide pH range between 2.0 and 10.0, although the removal efficiency was slightly higher in acidic conditions than that in basic conditions. Effects of background electrolyte and coexisting anions were not significant within the concentration ranges observed in high As groundwater. Results of XRD and Fe K-edge XANES analysis suggested ANS acted as an Fe(II)/(III) hybrid system, which was quite effective in adsorbing As from aqueous solution. There was no As redox transformation during adsorption, although Fe(II) oxidation occurred in the system. Two infrared bands at 787 and 872 cm^?1 after As(V) adsorption suggested that As(V) should be predominantly adsorbed on ANS via inner-sphere bidendate binuclear surface complexes.     

Thermodynamics of metal cation binding by a solid soil-derived humic acid: binding of Fe(III), Pb(II), and Cu(II)

Metal binding and release by solid humic acids (HAs) in soils and sediments can affect metal mobility and bioavailability. Isotherms for tight binding of Fe(III), Pb(II) and Cu(II) by a solid humic acid at pH2.0 fit the Langmuir binding model. Low pH was chosen to protonate the HA carboxylate groups and avoid metal cation hydrolysis. Binding of Fe(III), Pb(II) and Cu(II) occurs in one detectable step labeled A. Site capacities nu(A) are temperature-independent from 10.0 to 40.0 degrees C and point to binding by charge-neutralization to form solid complexes M(OOC-R)(n)(s), where n appears to be 2 for Pb(II) and 3 for Fe(III). Thermodynamic data pairs (DeltaH(A), DeltaS(A)) for metal binding are linearly correlated with previous data for Ca(II), Co(II) and Mg(II) binding by solid HAs.     

Adsorption behavior of reactive dye in aqueous solution on chemical cross-linked chitosan beads

A batch system was applied to study the adsorption of reactive dye (reactive red 189) from aqueous solutions by cross-linked chitosan beads. The ionic cross-linking reagent sodium tripolyphosphate was used to obtain more rigid chitosan beads. To stabilize chitosan in acid solutions, chemical cross-linking reagent epichlorohydrin (ECH), glutaraldehyde and ethylene glycol diglycidyl ether was used and ECH shows a higher adsorption capacity. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms at different particle sizes and isotherm constants were determined. The Langmuir model agrees very well with experimental data and its calculated maximum monolayer adsorption capacity has very large value of 1802-1840 (g/kg) at pH 3.0, 30 degrees C. The kinetics of the adsorption with respect to the initial dye concentration, temperature, pH, ionic strength, and wet/dry beads were investigated. The pseudo-first-order, second-order kinetic models and intraparticle diffusion model were used to describe the kinetic data and the rate constants were evaluated. The dynamical data fit well with the second-order kinetic model, except for the dry beads fitting better with the first-order model. The adsorption capacity increases largely with decreasing solution pH or with increasing initial dye concentration. Thermodynamic parameters such as change in free energy (deltaG(0)), enthalpy (deltaH(0)), entropy (deltaS(0)) and activation energy were also determined. The adsorption mechanism is shown to be the electrostatic interactions between the dye and chitosan beads. The desorption data shows that the removal percent of dye RR 189 from the cross-linked chitosan beads is 63% in NaOH solutions at pH 10.0, 30 degrees C. The desorbed chitosan beads can be reused to adsorb the dye and to reach the same capacity as that before desorption.     

A comparative study of the effects of chloride, sulfate and nitrate ions on the rates of decomposition of H2O2 and organic compounds by Fe(II)/H2O2 and Fe(III)/H2O2

The effects of chloride, nitrate, perchlorate and sulfate ions on the rates of the decomposition of hydrogen peroxide and the oxidation of organic compounds by the Fenton's process have been investigated. Experiments were conducted in a batch reactor, in the dark at pH < or = 3.0 and at 25 degrees C. Data obtained from Fe(II)/H2O2 experiments with [Fe(II)]0/[H2O2]0 > or = 2 mol mol(-1), showed that the rates of reaction between Fe(II) and H2O2 followed the order SO4(2-) > ClO4(-) = NO3- = Cl-. For the Fe(III)/H2O2 process, identical rates were obtained in the presence of nitrate and perchlorate, whereas the presence of sulfate or chloride markedly decreased the rates of decomposition of H2O2 by Fe(III) and the rates of oxidation of atrazine ([atrazine]0 = 0.83 microM), 4-nitrophenol ([4-NP]0 = 1 mM) and acetic acid ([acetic acid]0 = 2 mM). These inhibitory effects have been attributed to a decrease of the rate of generation of hydroxyl radicals resulting from the formation of Fe(III) complexes and the formation of less reactive (SO4(*-)) or much less reactive (Cl2(*-)) inorganic radicals.     

Immobilized Fe (III)-doped titanium dioxide for photodegradation of dissolved organic compounds in water

Photocatalytic degradation of dissolved organic carbon (DOC) by utilizing Fe(III)-doped TiO₂ at the visible radiation range is hereby reported. The photocatalyst was immobilized on sintered glass frits with the coating done by wet method, calcinated at 500 °C and then applied in a photodegradation reactor. The addition of a transition metal dopant, Fe(III), initiated the red shift which was confirmed by UV–Vis spectroscopy, and the photocatalyst was activated by visible radiation. X-ray diffraction patterns showed that Fe(III) doping had an effect on the crystallinity of the photocatalysts. Mixtures of DOC and associated coloured solutions were degraded in first-order kinetics, showing that the degradation process was not dependent on intermediates or other species in solution. A reactor with a catalyst coating area of 12.57 cm² was able to degrade 0.623 mg of the dissolved material per minute. Exposure of the reactor to hostile acidic conditions and repeated use did not compromise its efficiency. It was observed that the reactor regenerates itself in the presence of visible light, and therefore, it can be re-used for more than 100 runs before the performance dropped to <95 %. The results obtained indicate that the photocatalyst reactor has a great potential of application for use in tandem with biosorbent cartridges to complement water purification methods for domestic consumption.     

Photocatalytic degradation of methyl orange in aqueous suspension of mesoporous titania nanoparticles

The photodegradation of methyl orange (MO) was investigated in aqueous suspension containing titania nanoparticles with mesostructures (m-TiO(2)) under UV irradiation. The experimental results show that 98% MO can be mineralized in the 1.0 g l(-1) m-TiO(2) suspension (pH 2.0) after 45 min illumination. Particular attention was devoted to the identification and the transformation of the fragments retaining the chromophoric group. The photodegradation mechanism of the quinonoid MO mainly involves three intermedial processes: demethylation, methylation and hydroxylation. Among those processes, demethylation is more favorable than the hydroxylation, but the hydroxylation results in the largest number of intermediates. The degradation pathway of quinonoid MO under the optimal conditions is also proposed.     

Photodegradation of 4-tert octylphenol in aqueous solution promoted by Fe(III)

4-Tert-octylphenol (4-t-OP), a kind of endocrine-disrupting compounds, is widely distributed in natural water surroundings but can hardly be biodegraded. The advanced oxidation processes (AOPs) have been proved to be an efficient method to degrade 4-t-OP. In this study, the photodegradation of 4-t-OP in aqueous solution promoted by Fe(III) and the photooxidation mechanism were investigated. The ferric perchlorate was added into the aqueous solution for the production of hydroxyl radical. The efficiency of mineralization was monitored by total organic carbon analyzer, and photooxidation products were determined by high-performance liquid chromatography and liquid chromatography-mass spectrometer. 4-t-OP (2.4?×?10^?5 M) in aqueous solution was completely degraded after 45 min in the presence of Fe(III) (1.2?×?10^?3 M) under UV irradiation (λ?=?365 nm). The optimal pH was 3.5. Higher Fe(III) concentration or lower initial 4-t-OP concentration led to increased photodegradation efficiency of 4-t-OP. The reaction was almost completely inhibited in the presence of 2-propanol. About 70 % mineralization of the solution was obtained after 50 h. The photooxidation product was supposed to be 4-tert-octyl catechol. 4-t-OP in aqueous solution can be degraded in the presence of Fe(III) under the solar irradiation. The photoinduced degradation is due to the reaction with hydroxyl radicals. It shows that the 4-t-OP is mineralized by the inducement of Fe(III) aquacomplexes, which exposes to solar light. Therefore, the results would provide useful information for the potential application of the AOPs to remove 4-t-OP in water surroundings.     

A comparative study on the biosorption characteristics of some yeasts for Remazol Blue reactive dye

Biosorption capacities and rates of different kinds of dried yeasts (Saccharomyces cerevisiae, Schizosaccharomyces pombe, Kluyveromyces marxianus, Candida sp., C. tropicalis, C. lipolytica, C. utilis, C. quilliermendii and C. membranaefaciens) for Remazol Blue reactive dye from aqueous solutions were compared under laboratory conditions as a function of initial pH and initial dye concentration. Optimum initial biosorption pH was determined as 2 for all the yeasts. All the yeast species showed comparable and very high dye sorption at 100 mg/l initial dye concentration. The equilibrium sorption capacity of the biomass increased with increasing initial dye concentration up to 400 mg/l for Candida sp. C. lipolytica and C. tropicalis; up to 300 mg/l for C. quilliermendii and C. utilis and up to 200 mg/l for S. cerevisiae, S. pombe, K. marxianus and C. membranaefaciens while the adsorption yield of dye showed the opposite trend for all the yeasts. Among the nine yeast species, C. lipolytica exhibited the highest dye uptake capacity (Q(0) = 250 mg/g). Both the Freundlich and Langmuir adsorption models were found suitable for describing the biosorption of the dye by all the Candida yeasts (except C. membranaefaciens). The results indicated that the dye uptake process followed the pseudo-second-order kinetics for each dye-yeast system.