Photocatalytic degradation of cellulose bleaching effluent by supported TiO2 and ZnO

A cellulose bleaching effluent (E1) was degraded in batch conditions by photocatalysis using TiO2 and ZnO supported on glass Raschig rings. The effluent was completely decolourised and the total phenol content was reduced by 85% after 120 min treatment with both catalysts. Partial mineralization of the organic matter was confirmed by total organic carbon (TOC) reduction, approximately 50%. The residual organic matter shows a low acute toxicity as compared to the initial values and AOX values are strongly reduced after the photocatalytic oxidation. Molecular mass distribution showed that high molecular mass compounds were almost completely degraded.     

Post-treatment of bio-treated acrylonitrile wastewater using UV/Fenton process: degradation kinetics of target compounds

In this study, post-treatment of bio-treated acrylonitrile wastewater was performed using the UV/Fenton process. Five target compounds (furmaronitrile, 3-pyridinecarbonitrile, 1,3-dicyanobenzene, 5-methyl-1H-benzotriazole, and 7-azaindole) were selected as target compounds and their degradation kinetics were examined. Under optimal reaction conditions (H₂O₂ dosage 3.0 mM, Fe²⁺ dosage 0.3 mM, and initial pH 3.0), more than 85% of total organic carbon (TOC) was eliminated in 30 min when a 10-W UV lamp was employed, and the electrical energy per order of magnitude for TOC removal was as low as 2.96 kWh m^?3. Furthermore, the target compounds and the toxicity were largely removed from the bio-treated effluent. Size exclusion chromatography with organic carbon detector analysis revealed that organic components with a wide range of molecular weights were greatly reduced after the UV/Fenton process. A simplified pseudo steady-state (SPSS) model was applied to predict the degradation of target compounds during the UV/Fenton process. The concentrations of generated hydroxyl radicals were estimated to be 3.06 × 10^?12 M, 6.37 × 10^?12 M, and 10.9 × 10^?12 M under 5-, 10-, and 15-W UV lamps, respectively. These results demonstrate that the proposed SPSS model fitted well with experimental data on the post-treatment of real wastewater, and consequently indicate that this model can be a useful tool in the prediction of degradation of target compounds during the UV/Fenton process.

     

Mineralization of dinitrotoluenes and trinitrotoluene of spent acid in toluene nitration process by Fenton oxidation

Fenton's reagent, UV/H2O2 and UV/Fenton's reagent were employed to mineralize dinitrotoluene (DNT) isomers and 2,4,6-trinitrotoluene (TNT) of spent acid in toluene nitration process. The bench-scale experiments were conducted to elucidate the influence of various operating variables on the performance of removal of total organic compounds (TOC) from spent acid, including reaction temperature, concentration of ferrous ion and H2O2 dosage. It is remarkable that organic compounds were completely mineralized by Fenton oxidation, of which removal efficiency is superior to that of UV/H2O2. Nevertheless, it makes slight difference between Fenton oxidation and UV/Fenton oxidation. According to the spectra identified by gas chromatograph/mass spectrometer (GC/MS), it is proposed that oxidative degradation of DNT isomers leads to o-, m-, p-mononitrotoluene (MNT) and 1,3-dinitrobenzene respectively. Besides, the oxidation of 2,4,6-TNT gives the 1,3,5-trinitrobenzene intermediate. Apparently, Fenton oxidation is promising for purification of spent acid industrially.     

Effects of operating parameters on advanced oxidation of diuron by the Fenton's reagent: a statistical design approach

Advanced oxidation of diuron in aqueous solution by Fenton's reagent using FeSO(4) as source of Fe(II) was investigated in the absence of light. Effects of operating parameters namely the concentrations of pesticide (diuron), H(2)O(2) and Fe(II) on oxidation of diuron was investigated by using Box-Behnken statistical experiment design and the surface response analysis. Diuron oxidation by the Fenton reagent was evaluated by determining the total organic carbon (TOC), diuron, and adsorbable organic halogen (AOX) removals. Concentration ranges of the reagents resulting in the highest level of diuron oxidation were determined. Diuron removal increased with increasing H(2)O(2) and Fe(II) concentrations up to a certain level. Diuron concentration had a more profound effect than H(2)O(2) and Fe(II) in removal of diuron, TOC and AOX from the aqueous solution. Nearly complete (98.5%) disappearance of diuron was achieved after 15min reaction period. However, only 58% of diuron was mineralized after 240min under optimal operating conditions indicating formation of some intermediate products. Optimal H(2)O(2)/Fe(II)/diuron ratio resulting in the maximum diuron removal (98.5%) was found to be 302/38/20 (mgl(-1)).     

焦化废水泡沫分离液的Fenton催化氧化预处理

以焦化废水处理过程产生的泡沫分离液为研究对象，对其进行Fenton催化氧化处理实验，考察H₂O₂用量、Fe²⁺浓度、pH和反应时间4个因素对处理效果的影响，并结合GC/MS方法比较处理前后泡沫分离液中有机物的种类及其生物降解性的变化。结果表明，采用［H₂O₂］=100 mmol/L、［Fe²⁺］=100 mg/L、pH=3、反应时间为30 min的Fenton催化氧化反应条件，可以使分离液的COD去除率达到68%以上；经Fenton处理后，分离液的B/C值由0.12提高至0.38，生物降解性明显改善；通过GC/MS的分析，基本明确分离液中含有的有机物主要为酚、胺、腈、酯类有机物及喹啉、吡啶等杂环化合物，大多数属于难降解且生物毒性较强的有机物。针对这些复杂组分共存的泡沫分离液，利用Fenton试剂较强的氧化能力能够将其含有的有毒/难降解有机物转化为低毒或无毒的小分子有机物，为其后续的生物处理创造良好的条件。     

Kinetic degradation of the pollutant guaiacol by dark Fenton and solar photo-Fenton processes

This work is first intended to optimize the experimental conditions for the maximum degradation of guaiacol (2-methoxyphenol) by Fenton’s reagent, and second, to improve the process efficiency through the use of solar radiation. Guaiacol is considered as a model compound of pulp and paper mill effluent. The experiments were carried out in a laboratory-scale reactor subjected or not to solar radiation. Hydrogen peroxide solution was continuously introduced into the reactor at a constant flow rate. The kinetics of organic matter decay was evaluated by means of the chemical oxygen demand (COD) and the absorbance measurements. The experimental results showed that the Fenton and solar photo-Fenton systems lead successfully to 90% elimination of COD and absorbance at 604 nm from a guaiacol solution under particular experimental conditions. The COD removal always obeyed a pseudo-first-order kinetics. The effect of pH, temperature, H₂O₂ dosing rate, initial concentration of Fe²⁺, and initial COD was investigated using the Fenton process. The solar photo-Fenton system needed less time and consequently less quantity of H₂O₂. Under the optimum experimental conditions, the solar photo-Fenton process needs a dose of H₂O₂ 40% lower than that used in the Fenton process to remove 90% of COD.     

Fenton氧化对制浆造纸废水分子量及可生化性变化的影响

以制浆造纸废水的初沉池出水为研究对象,对不同剂量的Fenton氧化试剂处理制浆造纸厂初沉废水的效果进行了研究,初沉废水中的分子量大于10 000的有机污染物含量占到83%,废水可生化性较差;在Fe2+与H2O2的摩尔比为1∶5,废水pH为3.5的条件下,H2O2(30%)投加量小于3.25 mL/L时,Fenton试剂的氧化效率更高;H2O2(30%)投加量为6.50 mL/L时,废水中污染物的去除率更高,其中废水COD的去除率为79.5%,AOX的去除率为75.3%,色度去除率为97.5%,同时处理后废水中分子量在500~3 000之间的有机物含量占到82.98%,废水的BOD5/COD值提高到0.56。Fenton氧化作为前置技术处理制浆造纸废水,可以降低废水中的有机物分子量,减少废水的生物毒性,增加废水生物降解性,有助于后续生物处理的正常运行。     

Solar photodegradation of dichloroacetic acid and 2,4-dichlorophenol using an enhanced photo-Fenton process

The photo-Fenton process using potassium ferrioxalate as a mediator was investigated for the photodegradation of dichloracetic acid (DCA) and 2,4-dichlorophenol (DCP) in aqueous medium using solar light as source of irradiation. The influence of the solution depth, the light intensity and the effect of stirring the solution during irradiation process were evaluated using DCA as a model compound. A negligible influence of stirring the solution was observed when the concentration of ferrioxalate (FeOx) was 0.8 mM and solution depth was 4.5 or 14 cm. The optimum FeOx concentration determined for solution depths between 4.5 and 14 cm was 0.8 mM considering total organic carbon (TOC) removal during DCA irradiation. The high efficiency of the photo-Fenton process was demonstrated on summer days, when only 10 min of exposition (around noon) were sufficient to completely destroy the organic carbon of a 1.0 mM DCA solution in the presence of 0.8 mM FeOx and 6.0 mM H2O2 using a solution depth of 4.5 cm. It was observed that the photodegradation efficiency increases linearly with the solar light intensity up to values around 15 Wm(-2) but this linear relationship does not hold above this value showing a square root dependence. The photodegradation of a solution of DCP/FeOx showed a lower TOC removal rate than that observed for DCA/FeOx, achieving approximately 90% after 35 min irradiation under 19 W m(-2), while under this light intensity, the same TOC removal of DCA/FeOx was achieved in only 10 min irradiation.     

Applicability of Fenton and H2O2/UV reactions in the treatment of tannery wastewaters

In this paper we evaluated the H2O2/UV and the Fenton's oxidation processes for the treatment of tannery wastewater under different experimental conditions. Efficiencies were judged by the amounts of organic substances degraded or eliminated under these treatment techniques. Daphnia magna and Vibrio fischeri were used to monitor toxicity. Organic compounds contained in the untreated and treated tannery wastewater were determined and identified using substance specific techniques. Gas chromatography-mass spectrometry (GC-MS) in positive electron impact (EI(+)) mode was applied to determine volatile organics. Atmospheric pressure ionization (API) mass (MS) and tandem mass spectrometry (MS-MS) coupled with flow injection analysis (FIA) or liquid chromatography (LC) were used to detect or identify polar organic pollutants. The experimental results indicated that both oxidation processes--H2O2/UV at pH 3 and Fenton at pH 3.5--are able to reduce TOC content by mineralisation of the organic compounds.     

Comparative toxicity of effluents processed by different treatments in V79 fibroblasts and the algae Selenastrum capricornutum

The efficacy of ozonation and of photocatalysis processing in the treatment of pulp mill ECF (elementary chlorine free) bleaching and textile effluents was evaluated by determining total organic carbon reduction (TOC) and the toxicity. The chronic toxicity of the effluents was evaluated by the ability to inhibit the growth of algae Selenastrum capricornutum. Cultured hamster V79 fibroblasts were used to assess the cytotoxicity of effluents submitted to different detoxification processes. Two endpoints were measured in V79 cells: 3-(4,5-dimethylthiazole-2-yl)-2,5-biphenyl tetrazolium bromide (MTT) reduction and neutral red uptake (NRU). Both treatment processes were able to reduce the TOC, although ozonization was less effective for pulp mill ECF bleaching. The pulp mill ECF bleaching and textile effluents reduced the growth of S. capricornutum by 39% and 27%, respectively. However, at the highest concentration tested, the textile effluents treated by photochemical process for 60 min showed increased cytotoxicity in V79 cells compared to the untreated effluent when assessed by the NRU and MTT reduction assays (increases of 30% and 40%, respectively). Pulp mill ECF bleaching effluent treated by ozonization had a similar cytotoxicity to that of untreated effluent in the NRU assay. In contrast, the MTT reduction assay indicated that effluents treated with ozone were around 20% more cytotoxic than untreated effluents. These results show that cultured fibroblasts may be useful for studying cellular responses to pollutants and may be included in tests to monitor the efficiency of effluent detoxification processes.     

Identification and level estimation of chlorinated neutral aromatic sulfur compounds and their alkylated derivatives in pulp mill effluents and sediments

Seven effluent samples from a modern pulp mill, in which chlorine and chlorine dioxide bleaching is used, and five sediment samples from the recipient watercourse were investigated for polychlorinated dibenzothiophenes (PCDBTs), polychlorinated thianthrenes (PCTAs), polychlorinated diphenylsulfides (PCDPSs) and for alkylated derivatives of these. Mainly di-, tri-, tetra- and pentachlorinated congeners were studied. Particles and filtrates from the effluents were analyzed separately. The concentration levels of the nonalkylated compounds were found to be higher in the filtrates than in the particles. Trichlorinated dibenzothiophenes and thianthrenes were found as the major congeners. Pentachlorinated derivatives were not found. Alkylated di- and trichlorodibenzothiophenes were detected in some samples, while alkylated chlorinated thianthrenes and diphenylsulfides were nondetectable. The estimated concentration levels of the compounds detected were in the range of 40–2700 pg/L in the pulp mill effluents and in the range of 2–40 pg/g dry weight in the sediments. Mixtures of methylated di- and trichlorodibenzothiophenes used as references in analyses were prepared from methylchlorobiphenyls. Some new pure model compounds were obtained by HPLC fractionation of the chlorination mixture of dibenzothiophene. Structures of these were determined by ¹H NMR.     

Spectroscopic changes on fulvic acids from a kraft pulp mill effluent caused by sun irradiation

Large volumes of wastewater with a high organic load are generated by the pulp and paper industry that negatively affect the quality of receiving waters. The main waste products in the pulp mill effluents are lignin derived macromolecular compounds, which are similar to natural humic substances and very resistant to wastewater treatments. Fulvic acids (FA) represent the higher percentage of these humic substances and it was observed that solar irradiation modify their properties. Several analytic tools, namely, UV–Visible, molecular fluorescence and FTIR spectroscopies, were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. It may be concluded that sun irradiation may alter to a high extent the physicochemical properties of macromolecular organic matter, namely fulvic acids, released by kraft pulp mill effluents. After solar exposition, the aromaticity decreases, the aliphatic structures become more oxygenated, and the fulvic acids from the pulp mill effluent remaining in solution are more similar to aquatic fulvic acids from non polluted sites.     

Formation of organochlorine compounds in kraft pulp bleaching processes

The most abundant volatile organochlorine compounds (VOCCs), trichloroacetic and dichloroacetic acids and AOX, were determined in bleaching effluent and waste water from three kraft pulp mills during ClO₂ bleaching. 0.6–7.7 g of VOCCs per ton bleached pulp were formed, the most abundant being chloroform and dichloroacetic acid methyl ester. Most of the VOCCs were removed during treatment, and it was estimated that 2–30 t of VOCCs would be removed annually from activated sludge treatment plants in Finnish kraft pulp mills using elemental chlorine free bleaching, most likely by volatilization. Dichloroacetic acid was formed in considerably higher amounts than trichloroacetic acid, and both compounds were removed effectively during treatment. The formation of all organochlorine compounds decreased considerably when non-chlorinated bleaching was employed.     

Comparison of AC/O3-BAC and O3-BAC processes for removing organic pollutants in secondary effluent

AC (activated carbon)/O3-BAC (biological activated carbon) process was employed to treat secondary effluent and compared to O3-BAC process. The effects of ozone dosages and empty bed contact time (EBCT) in BAC on dissolved organic carbon (DOC) removal were investigated. The results showed that the presence of AC improved ozone utilization and biodegradability of the effluent. DOC removal increased with ozone dosage and EBCT in BAC, however, 3 mg l(-1) ozone dosage with 15 min oxidation time and 15 min EBCT in BAC were more economical and efficient. For DOC removal, AC/O3-BAC was more efficient than O3-BAC and its synergetic effect was more than that in O3-BAC process. The biomass of the subsequent BAC unit in AC/O3-BAC process was more than that in O3-BAC process and much more than that in BAC alone. Except for organic pollutants with molecular weight (MW) >10 kDa, those of other MW range were decomposed much more by AC/O3 process than by O3 process. GC/MS analysis showed that dibutyl phthalate, bis(2-ethylhexyl) phthalate, 4-bromo-3-chloroaniline, 2-propanone-ethylhydrazone and phenol derivatives were prevalent organic compounds in the secondary effluent. Some aromatic compounds, such as 4-bromo-3-chloroaniline and 2,4-dichloro-benzenamine disappeared after AC/O3 treatment. However, some small molecules were generated, after further biological treatment by BAC, the kinds and concentration of organic compounds were greatly reduced.     

Synthetic olive mill wastewater treatment by Fenton’s process in batch and continuous reactors operation

Degradation of total phenol (TPh) and organic matter, (expressed as total organic carbon TOC), of a simulated olive mill wastewater was evaluated by the Fenton oxidation process under batch and continuous mode conditions. A mixture of six phenolic acids usually found in these agro-industrial wastewaters was used for this purpose. The study focused on the optimization of key operational parameters of the Fenton process in a batch reactor, namely Fe²⁺ dosage, hydrogen peroxide concentration, pH, and reaction temperature. On the assessment of the process efficiency, > 99% of TPh and > 56% of TOC removal were attained when [Fe²⁺] = 100 ppm, [H₂O₂] = 2.0 g/L, T = 30 °C, and initial pH = 5.0, after 300 min of reaction. Under those operational conditions, experiments on a continuous stirred-tank reactor (CSTR) were performed for different space-time values (τ). TOC and TPh removals of 47.5 and 96.9%, respectively, were reached at steady-state (for τ = 120 min). High removal of COD (> 75%) and BOD₅ (> 70%) was achieved for both batch and CSTR optimum conditions; analysis of the BOD₅/COD ratio also revealed an increase in the effluent’s biodegradability. Despite the high removal of lumped parameters, the treated effluent did not met the Portuguese legal limits for direct discharge of wastewaters into water bodies, which indicates that coupled chemical-biological process may be the best solution for real olive mill wastewater treatment.     

不同来源高浓度有机废水的集中处理

按照水质情况,将多种来源于不同工业生产过程中的高浓度有机废水划分为高悬浮固体乳化液废水、难生化高浓度有机废水、高悬浮固体不含油有机废水、含铬有机废水和杂质含量较少的乳化液废水5类,分别采用酸化破乳/Fen-ton氧化/混凝/絮凝、Fenton氧化/混凝/絮凝、混凝/絮凝、还原/混凝/絮凝、震动膜过滤技术作为生化预处理技术,并通过小试和中试验证了各技术的效果。实验结果表明,按照上述分类结果,采用不同预处理技术可以得到良好的效果,废水水质明显改善,满足继续生化处理的基本条件。各预处理生产装置处理效果稳定,同时生化系统已经稳定运行120天以上,COD去除率超过90%,出水经过低剂量的Fenton试剂处理后可达到《污水排入城镇下水道水质标准》(CJ343-2012)。     

Analysis of volatile and semivolatile organic compounds in municipal wastewater using headspace solid-phase microextraction and gas chromatography.

The aim of this work was to develop a simple and fast analytical method for the determination of a wide range of organic compounds (volatile and semivolatile compounds) in municipal wastewater. The headspace-solid-phase microextraction (HS-SPME) and gas chromatography (with mass spectroscopy) was used for determination of the organic compounds. In this study, 39 organic compounds were determined, including 3 sulfur compounds, 28 substituted benzenes, and 8 substituted phenols. The extraction parameters, such as types of SPME fiber, extraction temperature, extraction time, desorption time, salt effect, and magnetic stirring, were investigated. The method had very good repeatability, because the relative standard deviations ranged from 0.5 to 12%. The detection limit of each compound was at or below the microgram-per-liter level. This method was applied for determination of the organic compounds in raw wastewater, primary effluent, secondary effluent, and chlorinated secondary effluent samples from the Chania Municipal Wastewater Treatment Plant (Crete, Greece).     

Chlorinated components in lime used in production contaminated citrus pulp pellets from Brazil

In order to further understand the contamination of the citrus pulp pellets (CPP) that were exported to Europe in 1997 we examined both contaminated lime and CPP samples for the distribution of polychlorinated biphenyls (PCBs) and chlorinated benzenes (tri–hexa). Standard isotope dilution techniques were applied for all samples, which were analysed by selected ion monitoring high resolution GC–MS. Lime that is used in the production of CPP product is highly contaminated with PCBs and chlorobenzenes.     

Semiconductor-assisted photodegradation of lignin, dye, and kraft effluent by Ag-doped ZnO

This work reports a preliminary study of semiconductor-assisted photochemical degradation of lignin, Remazol Brilliant Blue R and Kraft E1 paper effluent by using ZnO and Ag-doped ZnO photocatalysts. The doped semiconductor was prepared in the reaction media by photoreduction of silver nitrate. With the use of 100 mg of ZnO and 15 mg of Ag-ZnO, almost total decolorization of the dye and lignin samples in reaction times lower than 60 min were observed. Extending the photochemical reaction up to 120 min, the total organic carbon content (TOC) was reduced in 90%. For the paper effluent, a fast decolorization was obtained for relatively short reaction times. However, de TOC reduction was negligible (near of 10%) up to high reaction times (300 min). By using the Ag-ZnO photocatalyst, the toxicity of lignin and Kraft E1 effluent toward E. Coli was completely removed. For the dye, the formation of transient toxic species was observed.     

The role of ferrous ion in Fenton and photo-Fenton processes for the degradation of phenol

The efficiency of different Fenton-related oxidative processes such as Fenton, solar-Fenton and UV-Fenton were examined using phenol as a model compound in simulated and industrial wastewater. A batch study was conducted to optimize parameters like pH, hydrogen peroxide concentration and ferrous ion concentration governing the Fenton process. At optimum conditions, different Fenton-related processes were compared for the degradation of phenol. Increased degradation and mineralisation efficiency were observed in photo-Fenton processes as compared to conventional Fenton process. The maximum mineralising efficiency for phenol with Fenton, solar and UV-Fenton processes were 41%, 96% and 97% respectively. In Fenton process, carboxylic acids like acetic acid and oxalic acid were formed as end products during the degradation of phenol while in photo-Fenton processes, both these ions were identified during the early stages of phenol degradation and were oxidized almost completely at 120 min of the reaction time. In photo-Fenton processes (solar and UV light) complete degradation were observed with 0.4 mM of Fe2+ catalyst as compared to 0.8 mM of Fe2+ in conventional Fenton process. In Fenton and solar-Fenton processes, an iron reusability study was performed to minimize the amount of iron used in treatment process. The efficacy of Fenton and solar-Fenton processes was applied to effluent from phenol resin-manufacturing unit for the removal and mineralisation of phenol.