Comparative studies of the Fe3+/2+-UV, H2O2-UV, TiO2-UV/vis systems for the decolorization of a textile dye X-3B in water

The degradation of a common textile dye, Reactive-brilliant red X-3B, by several advanced oxidation technologies was studied in an air-saturated aqueous solution. The dye was resistant to the UV illumination (wavelength λ  320 nm), but was decolorized when one of Fe³⁺, H₂O₂ and TiO₂ components was present. The decolorization rate was observed to be quite different for each system, and the relative order evaluated under comparable conditions followed the order of Fe²⁺–H₂O₂–UV  Fe²⁺–H₂O₂ > Fe³⁺–H₂O₂–UV > Fe³⁺–H₂O₂ > Fe³⁺–TiO₂–UV > TiO₂–UV > Fe³⁺–UV > TiO₂–visible light (λ  450 nm) > H₂O₂–UV > Fe²⁺–UV. The mechanism for each process is discussed, and linked together for understanding the observed differences in reactivity.     

Degradation of aquatic humic material by ultraviolet light

Natural humic water was treated with ultraviolet (UV) light and UV + hydrogen peroxide (UV/H₂O₂. The effects on the dissolved organic carbon content (DOC), the UV-absorbance at 254 nm (UV-abs.), the molecular size distribution, pH, and mutagenic activity were monitored, and the identity and concentrations of the most abundant gas chromatographable organic degradation products were determined.

The DOC content and the UV-abs. of the water decreased substantially during treatment with UV/H₂O₂. The decreases were dependent on the time of irradiation (UV dose) as well as on the H₂O₂ dose applied. The humus macromolecules were degraded to smaller fragments during irradiation. At higher UV doses, however, part of the dissolved organic matter (DOM) was found to precipitate, probably as a result of polymerization. Oxalic acid, acetic acid, malonic acid, and n-butanoic acid were the most abundant degradation products detected. These acids were found to account for up to 20% and 80% of the DOM in UV- and UV/H₂O₂-treated waters, respectively. No mutagenic activity was generated by the UV irradiation or the UV/H₂O₂ treatment. It is further concluded that the substantial mutagenic activity formed during chlorination of humic waters cannot be decreased by using UV irradiation as a pretreatment step.     

硝基苯类废水的全混态零价铁-芬顿组合预处理工艺优化与工程验证

针对企业硝基氯苯装置产生的高毒性、难降解的硝基苯类废水,开发出全混态零价铁-芬顿组合预处理工艺,并分别优化了零价铁还原和芬顿氧化的工艺条件。结果表明,pH为2.0、零价铁投加量为220 mg/L时,废水中硝基苯类物质的去除率可达98.5%以上。出水pH约为3.0,继续投加3000 mg/L的H₂O₂,Fe²⁺投加比按C(Fe²⁺,mg/L):C(H₂O₂,mg/L)=1:10,1 h内COD去除率可达90%以上,且B/C由0.08提高到0.45。可见该组合预处理工艺可大幅削减废水毒性、改善可生化性,且直接运行成本仅为26.28元/吨,具有良好的环境和经济效益。     

Fenton''s type reaction and chemical pretreatment of PCBs

This study evaluates the effects of Fenton's reagent (FR) on the rate and extent of the oxidative degradation of individual mono, di-, tri- and tetrachlorobiphenyls in the commercial mixture DELOR 103, equivalent to AROCLOR 1248. The oxidation effect of FR strongly increased with increasing the molar ratio of Fe²⁺/H₂O₂. The most effective oxidation of DELOR 103 (10 μg.ml⁻¹) was achieved in a solution containing 1M H₂O₂ and 1 mM Fe²⁺. The FR elimination rate constants of PCB congeners decrease with increasing number of chlorine substituents in the biphenyl molecule and show a good correlation with the values of molecular weights of the PCB congeners and their 1-octanol/water partition coefficients.     

Comparative study of the oxidation of atrazine and acetone by H2O2/UV, Fe(III)/UV, Fe(iii)/H2O2/UV and Fe(II) or Fe(III)/H2O2

In this study, the rates of degradation of organic compounds by several AOPs (H₂O₂/UV, Fe(III)/UV, Fe(III)/H₂O₂/UV, Fe(II)/H₂O₂ and Fe(III)/H₂O₂) have been compared. Experiments were carried out at pH ≈ 3 (perchloric acid / sodium perchlorate solutions) and with UV reactors equipped with a low-pressure mercury vapour lamp (emission at 253.7 run). The data obtained with atrazine ([Atrazine]_o = 100 μg/L) showed that the rate of degradation of atrazine in very dilute aqueous solution is much more rapid with Fe(III)/UV than with H₂O₂/UV. Photo-Fenton process (Fe(III)/H₂O₂/UV) was found to be more efficient than H₂O₂/UV and Fe(II)/H₂O₂ for the mineralization of acetone ([Acetone]_o = 1 mM).     

A hybrid fenton oxidation-microbial treatment for soil highly contaminated with benz(a)anthracene

In order to mitigate the strong microbial resistance of benz(a)anthracene [B(a)A] in soil, a hybrid treatment of Fenton oxidation followed microbial culture was carried out. Based on optimal Fenton oxidation, i.e., 1.0 ml of ethanol, 0.2 ml of 0.5 M Fe²⁺, and 0.3 ml of 30% H₂O₂ per 1 g of 500 mg B(a)A/kg soil, about 43% of B(a)A-7,12-dione was generated during oxidation of 97% B(a)A. When the comparative biodegradability between B(a)A-contaminated soil and B(a)A-contaminated soil after Fenton oxidation was examined, it was found that 98% of B(a)A-7,12-dione degraded after 63 d in comparison with only 12% of B(a)A over the same period; results demonstrating that Fenton oxidation enhances biodegradability of B(a)A through B(a)A-7,12-dione.     

沼渣生物炭基Fenton催化剂的制备及其高效降解吡虫啉农药废水的研究

以废弃物沼渣和含铁剩余污泥为原料,采用一步热解法制备沼渣生物炭基Fenton催化剂(以下简称催化剂),构建了非均相Fenton反应体系处理含吡虫啉模拟废水,考察了H2 O2和催化剂用量对吡虫啉去除率的影响.结果表明,非均相Fenton反应体系中,H2 O2最佳投加量为0.50 g/L,催化剂最佳投加量为1.00 g/L...     

Sequential photochemical-biological degradation of chlorophenols

UV/TiO₂/H₂O₂, UV/TiO₂ and UV/H₂O₂ were compared as pre-treatment processes for the detoxification of mixtures of 4-chlorophenol (4CP), 2,4-dichlorophenol (DCP), 2,4,6-trichlorophenol (TCP) and pentachlorophenol (PCP) prior to their biological treatment. When each chlorophenol was initially supplied at 50 mg l⁻¹, UV/TiO₂/H₂O₂ treatment supported the highest pollutant removal, COD removal, and dechlorination efficiencies followed by UV/TiO₂ and UV/H₂O₂. The remaining toxicity to Lipedium sativum was similar after all pre-treatments. Chlorophenol photodegradation was always well described by a first order model kinetic (r² > 0.94) and the shortest 4CP, DCP, TCP and PCP half-lives of 8.7, 7.1, 4.5 and 3.3 h, respectively, were achieved during UV/TiO₂/H₂O₂ treatment. No pollutant removal was observed in the controls conducted with H₂O₂ or TiO₂ only. Inoculation of all the photochemically pre-treated mixtures with activated sludge microflora was followed by complete removal of the remaining pollutants. Combined UV/TiO₂/H₂O₂-biological supported the highest detoxification, dechlorination (99%) and COD removal (88%) efficiencies. Similar results were achieved when each chlorophenol was supplied at 100 mg l⁻¹. COD and Cl mass balances indicated UV, UV/H₂O₂, and UV/TiO₂ treatments lead to the formation of recalcitrant photoproducts, some of which were chlorinated.     

Optimizing electron spin resonance detection of hydroxyl radical in water

The parameters affecting the electron spin resonance (ESR) detection of hydroxyl free radical in water are studied and optimized. The hydroxyl radical is generated by the Fenton reaction with iron (II) ammonium sulfate and hydrogen peroxide reacting in a phosphate buffer using N-tert-butyl-alpha-phenylnitron as the spin trap. The concentrations of Fe²⁺, H₂O₂, and phosphate buffer are the parameters studied. The Taguchi method and the orthogonal experiment design were used to evaluate the effects of these parameters on the ESR signal intensity. By the analysis of the signal-to-noise ratio and the analysis of variance, the order of importance of the various parameters on the hydroxyl radical formation is determined for optimal ESR detection of hydroxyl radical. The results will help the development of water purification technologies using hydroxyl free radical as a green oxidant.     

Pulsed discharge plasma induced Fenton-like reactions for the enhancement of the degradation of 4-chlorophenol in water

To sufficiently utilize chemically active species and enhance the degradation rate and removal efficiency of toxic and biorefractory organic pollutant para-chlorophenol (para-CP), the introductions of iron metal ions (Fe²⁺/Fe³⁺) into either pulsed discharge plasma (PDP) process or the PDP process with TiO₂ photo-catalyst were tentatively performed. The experimental results showed that under the same experimental condition, the degradation rate and removal efficiency of para-CP were greatly enhanced by the introduction of iron ions (Fe²⁺/Fe³⁺) into the PDP process. Moreover, when iron ions and TiO₂ were added together in the PDP process, the degradation rate and removal energy of para-CP further improved. The possible mechanism was discussed that the obvious promoting effects were attributed to ferrous ions via plasma induced Fenton-like reactions by UV light irradiation excited and hydrogen peroxide formed in pulsed electrical discharge, resulting in a larger amount of hydroxyl radicals produced from the residual hydrogen peroxide. In addition, the regeneration of ferric ions to ferrous ions facilitates the progress of plasma induced Fenton-like reactions by photo-catalytic reduction of UV light, photo-catalytic reduction on TiO₂ surface and electron transfer of quinone intermediates, i.e. 1,4-hydroquinone and 1,4-benzoquinone.     

UV-H2O2 based AOP and its integration with biological activated carbon treatment for DBP reduction in drinking water

The presence of disinfection byproducts (DBPs) such as trihalomethanes (THMs) and haloacetic acids (HAAs) in drinking water is of great concern due to their adverse effects on human health. Emerging regulation limiting the concentration of DBPs in drinking water has increased demands for technologies and processes which reduce the formation of DBPs in drinking water. In this study, UV-H₂O₂ based advance oxidation process (AOP) was used to treat raw surface water. Experiments were conducted using low pressure mercury vapor UV lamps in collimated beam and flow-through annular photoreactors. The effect of UV fluence (0–3500 mJ cm⁻²) and hydrogen peroxide concentration (0–23 mg l⁻¹) in reducing the concentration of THMs and HAAs was examined. The UV-H₂O₂ AOP was then coupled with a downstream biological activated carbon (BAC) treatment to assess the synergetic benefits of combining the two treatments. It was observed that UV-H₂O₂ AOP was only effective at reducing DBPs at UV fluences of more than 1000 mJ cm⁻²and initial H₂O₂ concentrations of about or greater than 23 mg l⁻¹. However, the combined AOP–BAC treatment showed significant reductions of 43%, 52%, and 59% relative to untreated raw water for DBPs, TOC, and UV₂₅₄, respectively.     

Fe and UV-enhanced ozonation of chlorophenolic compounds in aqueous medium

Mono-, di- and trichlorophenol including different isomers were degraded by O₃, O₃ + UV and O₃ + UV + Fe³⁺. Disappearance rates are nearly identical among three ozonations. Whereas TOC elimination was not completed by ozone alone. UV illumination accelerated TOC elimination rate and the addition of Fe³⁺ (O₃ + UV + Fe³⁺) further accelerated it. TOC elimination rates among different chlorophenols were in the order of mono > di > tri. The effect of Fe³⁺ was largest on the degradation of trichlorophenol. Hydroxylated aromatics, organic acids, formaldehyde and acetone were detected as intermediates.     

Photocatalytic degradation of phenol by visible light-responsive iron-doped TiO2 and spontaneous sedimentation of the TiO2 particles

Fe-doped TiO₂ was prepared by the calcination of Fe_xTiS₂ (x = 0, 0.002, 0.005, 0.008, 0.01) and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV–visible diffuse reflectance spectra. All the Fe-doped TiO₂ were composed of an anatase crystal form and showed red shifts to a longer wavelength. The activity of the Fe-doped TiO₂ for the degradation of phenol was investigated by varying the iron content during UV (365 nm) and visible light (405 nm and 436 nm) irradiation. The degradation rate depended on the Fe content and the Fe-doped TiO₂ was responsive to the visible light as well as the elevated activity toward UV light. The molar ratio of 0.005 was the optimum for both the UV and visible light irradiations. The result was discussed on the basis of the balance of the excited electron–hole trap by the doped Fe³⁺ and their charge recombination on the doped Fe³⁺ level. The Fe-doped TiO₂ (x = 0.005) was more active than P25 TiO₂ under solar light irradiation. The suspended Fe-doped TiO₂ spontaneously precipitated once the stirring of the reaction mixture was terminated.     

Modified Fenton reaction for trichlorophenol dechlorination by enzymatically generated H2O2 and gluconic acid chelate

Glucose oxidase is a well-known enzyme that catalyzes the oxidation of β-d-glucose to produce gluconic acid and hydrogen peroxide. Fenton reaction is a powerful oxidation technology used for the oxidation of groundwater pollutants. For the application of Fenton reaction in groundwater remediation, successful operation of Fenton reaction near neutral pH, and on-site generation of both H₂O₂ and chelate will be beneficial. The focus of this experimental study was to couple the glucose oxidation reaction with chelate-based Fenton reaction. The idea was to use the hydrogen peroxide and chelate gluconic acid generated during glucose oxidation for the dechlorination of 2,4,6-trichlorophenol (TCP) by Fenton reaction. The oxidation of glucose was achieved using the enzyme in free and immobilized forms. The rate of production of hydrogen peroxide was determined for each system, and was used to estimate the time required for complete consumption of glucose during the process, thus avoiding any traces of glucose in the Fenton reaction. In the case of free enzyme reaction, separation of the enzyme was achieved using an ultrafiltration membrane before initiating the Fenton reaction. The oxidation of TCP by Fenton reaction was performed at varying ratios of gluconic acid/Fe, and its effect on the decomposition of TCP and H₂O₂ was studied. TCP degradation was studied both in terms of parent compound degradation and free chloride generation.     

Decolorizing of lignin wastewater using the photochemical UV/TiO2 process

Studies on applying the photochemical UV/TiO2 oxidation process to treat the lignin-containing wastewater for dissolved organic carbon (DOC), color and reducing A254 (the absorption at the wavelength of 254 nm) have been carried out. The data obtained in this study demonstrate that the UV/TiO2 process is effective in oxidizing the lignin thus reducing the color and DOC of the wastewater treated. The combined UV/TiO2 treatment can achieve better removal of DOC and color than the UV treatment alone. Color removal, based on American Dye Manufacture Index (ADMI) measurement, is greater than 99% if the pH is maintained at 3.0 with the addition of 1 g l(-1) TiO2. When 10 g l(-1) TiO2 is applied, the oxidation reduction potential (ORP) value is reached to result in an 88% removal of both DOC and color. A model was developed based on the variation of ORP during the photochemical reaction to simulate the decoloring process. The proposed model can be used to predict the color removal efficiency of the UV/TiO2 process.     

Influence of redox mediators and metal ions on synthetic acid dye decolourization by crude laccase from Trametes hirsuta

In this paper, the effect of redox mediators on synthetic acid dye decolourization (Sella Solid Red and Luganil Green) by laccase from Trametes hirsuta cultures has been investigated. All the redox mediators tested, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), 1-hydroxybenzotriazole (HBT) and Remazol Brilliant Blue R (RBBR), led to higher activities than those obtained without mediators addition showing the suitability of the laccase/mediator system (LMS) in the decolourization of acid dyes. HBT was by far the most effective mediator, showing a decolourization percentage of 88% in 10 min for Sella Solid Red and of 49% in 20 min for Luganil Green. On the other hand, the stability of laccase against several metal ions, normally found in textile wastewater, was assessed. Laccase was stable at a concentration of 1mM for 7d against all the metal ions tested except for Zn+2, CrO4(-2), Cd+2, Cr2O7(-2), Fe+2, Cu+2 and especially Hg+2. When the concentration was increased to 10mM laccase stability decreased against all the metals assayed, in particular against Fe+2. In addition, the effect of metal ions on the decolourization process was also studied. It was found that Hg+2 inhibited the dye decolourization process, being the presence of HBT absolutely required for dye decolourization.     

不同老化条件对聚酰胺6微塑料吸附磺胺噻唑的影响

聚酰胺类微塑料(PA-MPs)和磺胺类抗生素(SAs)均为新兴污染物且已广泛检出,其中聚酰胺6微塑料由常用的聚酰胺6塑料产生,磺胺噻唑(ST)是典型的SAs.由于微塑料在环境暴露中普遍易老化,因此探究了聚酰胺6微塑料在未老化、紫外老化、紫外和H2 O2老化(分别记为PA6、PA6-UV、PA6-UV+H2 O2)下对S...     

Photocatalytic bacterial inactivation by polyoxometalates

The photocatalytic inactivation (PCI) of Escherichia coli (Gram-negative) and Bacillus subtilis (Gram-positive) was performed using polyoxometalate (POM) as a homogeneous photocatalyst and compared with that of heterogeneous TiO₂ photocatalyst. Aqueous suspensions of the microorganisms (10⁷–10⁸ cfu ml⁻¹) and POM (or TiO₂) were irradiated with black light lamps. The POM-PCI was faster than (or comparable to) TiO₂-PCI under the experimental conditions employed in this study. The relative efficiency of POM-PCI was species-dependent. Among three POMs (H₃PW₁₂O₄₀, H₃PMo₁₂O₄₀, and H₄SiW₁₂O₄₀) tested in this study, the inactivation of E. coli was fastest with H₄SiW₁₂O₄₀ while that of B. subtilis was the most efficient with H₃PW₁₂O₄₀. Although the biocidal action of TiO₂ photocatalyst has been commonly ascribed to the role of photogenerated reactive oxygen species such as hydroxyl radicals and superoxides, the cell death mechanism with POM seems to be different from TiO₂-PCI. While TiO₂ caused the cell membrane disruption, POM did not induce the cell lysis. When methanol was added to the POM solution, not only the PCI of E. coli was enhanced (contrary to the case of TiO₂-PCI) but also the dark inactivation was observed. This was ascribed to the in situ production of formaldehyde from the oxidation of methanol. The interesting biocidal property of POM photocatalyst might be utilized as a potential disinfectant technology.     

Effects of Fe2O3, organic matter and carbonate on photocatalytic degradation of lindane in the sediment from the Liao River,China

Fourteen sediment samples with different content of Fe₂O₃ were collected from the lower reaches of the Liao River in China. The photodegradation of lindane on the surfaces of these sediments was investigated to observe the effects of Fe₂O₃ and other photoinducable substances, such as TiO₂ and organic substances, on photodegradation of lindane. A partial least-squares (PLS) analysis model was developed to find out the statistical relationship between the photodegradation and the contents of these photoinducable substances. It was concluded from the PLS analysis that inorganic carbon and organic carbon have negative effects, whereas Fe₂O₃ and TiO₂ accelerate the photodegradation of lindane in the sediment samples when 365 nm UV light was used as light source. In all cases of the experiments, the photodegradation of lindane in the sediment samples were fitted for pseudo-first-order kinetics.     

Experimental design of Fenton and photo-Fenton reactions for the treatment of cellulose bleaching effluents

Multivariate experimental design was applied to the treatment of a cellulose conventional bleaching effluent in order to evaluate the use of the Fenton reagent under solar light irradiation. The effluent was characterised by the general parameters total organic carbon (TOC), chemical oxygen demand and color, and it was analysed for chlorinated low molecular weight compounds using GC–MS. The main parameters that govern the complex reactive system: Fe(II) and H₂O₂ initial concentration, and temperature were simultaneously studied. Factorial experimental design allowed to assign the weight of each variable in the TOC removal after 15 min of reaction. Temperature had an important effect in the organic matter degradation, especially when the ratio of Fenton reagents was not properly chosen. Fenton reagent under solar irradiation proved to be highly effective for these types of wastewaters. A 90% TOC reduction was achieved in only 15 min of treatment. In addition, the GC–MS analysis showed the elimination of the chlorinated organic compounds initially detected in the studied bleaching effluents.