Enhanced sludge solubilization by microbubble ozonation

A microbubble ozonation process for enhancing sludge solubilization was proposed and its performance was evaluated in comparison to a conventional ozone bubble contactor. Microbubbles are defined as bubbles with diameters less than several tens of micrometers. Previous studies have demonstrated that microbubbles could accelerate the formation of hydroxyl radicals and hence improve the ozonation of dyestuff wastewater. The results of this study showed that microbubble ozonation was effective in increasing ozone utilization and improving sludge solubilization. For a contact time of 80 min, an ozone utilization efficiency of more than 99% was obtained using the microbubble system, while it gradually decreased from 94% to 72% for the bubble contactor. The rate of microbial inactivation was obviously faster in the microbubble system. At an ozone dose of 0.02 g O₃ g⁻¹ TSS, about 80% of microorganisms were inactivated in the microbubble system, compared with about 50% inactivation for the bubble contactor. Compared to the bubble contactor, more than two times of COD and total nitrogen, and eight times of total phosphorus content were released from the sludge into the supernatant by using the microbubble system at the same ozone dosage. The application of microbubble technology in ozonation processes may provide an effective and low cost approach for sludge reduction.     

微气泡曝气中氧传质特性研究

气泡曝气过程中氧传质对于好氧生物处理过程具有重要意义。采用水力旋转剪切微气泡发生装置,考察了运行条件和水质特性对微气泡曝气中氧传质特性的影响。结果表明,微气泡曝气可获得较高的气含率和气泡停留时间;表面活性剂十二烷基磺酸钠(SDS)可以提高微气泡曝气的气含率和气泡停留时间。微气泡曝气中氧的总体积传质系数明显高于传统气泡曝气。总体积传质系数随着空气流量的增加而增加;氧传质效率随着空气流量的增加而减小,且对空气流量的变化更为敏感。在温度15~35℃范围内,微气泡曝气中氧的总体积传质系数随着温度的增加而增加,变化关系与传统气泡曝气基本相同,但对温度的变化更为敏感。微气泡曝气中,表面活性剂SDS会使氧的总体积传质系数略有降低,其不利影响明显小于传统气泡曝气;氧的总体积传质系数随盐度(NaC l浓度)增加而逐渐增加,并在NaC l浓度5 000 mg/L后趋于稳定。     

The photocatalytic degradation of methylene blue by green semiconductor films that is induced by irradiation by a light-emitting diode and visible light

This study develops a low-energy rotating photocatalytic contactor (LE-RPC) that has Cu-doped TiO₂ films coated on stainless-steel rotating disks, to experimentally evaluate the efficiency of the degradation and decolorization of methylene blue (MB) under irradiation from different light sources (visible 430 nm, light-emitting diode [LED] 460 nm, and LED 525 nm). The production of hydroxyl radicals is also examined. The experimental results show that the photocatalytic activity of TiO₂ that is doped with Cu²⁺ is induced by illumination with visible light and an LED. More than 90% of methylene blue at a 10 mg/L concentration is degraded after illumination by visible light (430 nm) for 4 hr at 20 rpm. This study also demonstrates that the quantity of hydroxyl radicals produced is directly proportional to the light energy intensity. The greater the light energy intensity, the greater is the number of hydroxyl radicals produced.

Implications: The CuO-doped anatase TiO₂ powder was successfully synthesized in this study by a sol–gel method. The catalytic abilities of the stainless-steel film were enhanced in the visible light regions. This study has successfully modified the nano-photocatalytic materials to drop band gap and has also successfully fixed the nano-photocatalytic materials on a substratum to effectively treat dye wastewater in the range of visible light. The results can be useful to the development of a low-energy rotating photocatalytic contactor for decontamination purposes.     

Characterization of a simple bacterial consortium for effective treatment of wastewaters with reactive dyes and Cr(VI)

A microbial consortia consisting of three bacteria isolated from tanning and textile wastewaters revealed high capacity to simultaneously bioaccumulate dye and Cr(VI). The identity of the bacteria were determined by 16S rRNA gene analysis to be closely related to Ochrobactrium sp., Salmonella enterica and Pseudomonas aeruginosa. Dependence of initial pH values and range of concentrations of the dye Reactive Black B (33.2-103.1 mg l(-1)) and Cr(VI) (19.9-127.6 mg l(-1)) were examined to find the effect of pH on the dye and Cr(VI) bioaccumulation. Optimal pH for growth of the consortia in media containing 35 mg l(-1) dye and 50 mg l(-1) Cr(VI) was determined to be around 8. The Cr(VI) bioaccumulation by the consortia was rapid in media containing molasses with or without reactive dye with a maximum Cr(VI) bioaccumulation yield ranging from 90% to 99% within a 2-4d period. A slightly lower yield for the dye bioaccumulation was measured with a maximum dye bioaccumulation of 80% at 59.3 mg l(-1) dye and 69.8 mg l(-1) Cr(VI). The highest specific Cr uptake value was obtained as 76.7 mg g(-1) at 117.1 mg l(-1) Cr(VI) and 50.8 mg l(-1) dye concentration. This ability to bioaccumulate dye and Cr(VI) was more efficient than the enriched sludge from which they were isolated.     

Microbial degradation of phenol in high-salinity solutions in suspensions and hollow fiber membrane contactors

A microporous polypropylene (PP) hollow fiber membrane contactor was used as a bioreactor to degrade phenol in aqueous solutions by Pseudomonas putida BCRC 14365 at 30 degrees C. The fibers were pre-wetted by ethanol to make them more hydrophilic. The initial cell density was fixed at 0.025 gl(-1). The effects of added NaCl concentration (0-1.78 M) and pH (3-8) in substrate solution on the biodegradation were studied. The experimental results by suspended cells were discussed. It was shown that the cells in microporous hollow fibers were unable to tolerate substrate solution pH to a larger range than those in suspensions. The suspended cells grew well on 100 mg l(-1) of phenol only at NaCl concentrations below 0.44 M. However, the cells in microporous hollow fibers could completely degrade 500 mg l(-1) of phenol in solutions containing NaCl concentration up to 1.52 M, which was due to the enhanced tolerance limit to salinity effect by the membrane-attached biofilms and the sufficiently slow mass transfer of NaCl through the membrane pores.     

Decolorization of synthetic dyes using a copper complex with glucaric acid

Selected azo, acridine, triphenyl methane, anthraquinone and thiazine-based dyes were decolorized using a catalytic system consisting of Cu(II)/glucaric acid/H(2)O(2). More than 90% decolorization was obtained with 100 ppm Acridine Orange, Azure B, Chicago Sky Blue, Crystal Violet, Methyl Orange, Poly B-411, Reactive Black 5, Reactive Blue 2, and Remazol Brilliant Blue R within 24 h. Seventy to eighty percent decolorization was achieved within the first 6 h. The decolorizaton was not affected by pH. The involvement of hydroxyl radicals produced in the system in the decolorization of the dye molecules was confirmed by electron spin resonance study.     

Activated carbon from industrial solid waste as an adsorbent for the removal of Rhodamine-B from aqueous solution: kinetic and equilibrium studies

The activated carbon was prepared using industrial solid waste called sago waste and physico-chemical properties of carbon were carried out to explore adsorption process. The effectiveness of carbon prepared from sago waste in adsorbing Rhodamine-B from aqueous solution has been studied as a function of agitation time, adsorbent dosage, initial dye concentration, pH and desorption. Adsorption equilibrium studies were carried out in order to optimize the experimental conditions. The adsorption of Rhodamine-B onto carbon followed second order kinetic model. Adsorption data were modeled using both Langmuir and Freundlich classical adsorption isotherms. The adsorption capacity Q0 was 16.12 mg g(-1) at initial pH 5.7 for the particle size 125-250 microm. The equilibrium time was found to be 150 min for 10, 20 mg l(-1) and 210 min for 30, 40 mg l(-1) dye concentrations, respectively. A maximum removal of 91% was obtained at natural pH 5.7 for an adsorbent dose of 100mg/50 ml of 10 mg l(-1) dye concentration and 100% removal was obtained when the pH was increased to 7 for an adsorbent dose of 275 mg/50 ml of 20 mg l(-1) dye concentration. Desorption studies were carried out in water medium by varying the pH from 2 to 10. Desorption studies were performed with dilute HCl and show that ion exchange is predominant dye adsorption mechanism. This adsorbent was found to be both effective and economically viable.     

Photooxidation of the phenylazonaphthol AO20 on TIO2: kinetic and mechanistic investigations.

The results of the photocatalytic and photosensitized degradations of the monoazo dye AO20 in aqueous solution using suspended titanium dioxide are presented. Kinetic and mechanistic details have been elucidated using UV/Vis, FTIR and TCO techniques. It was proven that adsorption of dye molecules onto the support material is essential for the processes to be effective. Moreover, even if their mechanisms differ during the early stages, photocatalysis and photosensitization lead to very similar ultimate breakdown products. Indeed, the original dye anchored to the oxide surface systematically undergoes fast decomposition until it is transformed into CO2 or aliphatic acids (formic, acetic, oxalic acids), which react rather slowly with hydroxyl radicals or trapped holes.     

Kinetics of oxidative decolorization and mineralization of Acid Orange 7 by dark and photoassisted Co2+-catalyzed peroxymonosulfate system

A kinetic model was proposed and used to interpret the experimental data for degradation of Acid Orange 7 (AO7) in aqueous solution induced by Co(2+)/peroxymonosulfate (Co/PMS) reagent in terms of both decolorization and mineralization. The pseudo first-order decolorization rate constants are related to [Co(2+)], [PMS], reciprocal of [H(+)] and [AO7](0). Activation energy of the AO7 decolorization process was determined to be 75.7 kJ mol(-1). UV and visible light can accelerate the decolorization and mineralization process due to different mechanisms. In the combined UV/Co/PMS system, UV light can decompose PMS to generate hydroxyl ((*)OH) and sulfate radicals (SO(4)(*-)), while in the Vis/Co/PMS system, excited AO7 molecules can transfer electrons to PMS or Co(3+) and thus accelerate the decomposition of PMS and catalytic cycle of Co(3+)/Co(2+).     

Concentrations and distribution of 3,3'-dichlorobenzidine and its congeners in environmental samples from Lake Macatawa

Release of 3,3'-dichlorobenzidine (DCB), an intermediate in dye manufacturing processes, is of environmental concern due to its carcinogenic nature. An 11-year field study has been conducted to elucidate the fate and behavior of DCB and its congeners in the Lake Macatawa (Holland, MI, USA) sediment-water system. The sediments were variable in composition, ranging from sandy sediments with 1-8.7% total organic carbon (OC) to silty-clay sediments with 7.5-20.6% total OC. The pH ranged from 6.3 to 7.4. The findings from this field study confirmed that DCB and its congener, benzidine, are transported over long distances. The concentration of DCB in the water phase was found to be from non-detectable to approximately 1300 times greater than the water quality criteria established for DCB (0.021 microg/l). Its congener, benzidine, which is substantially more toxic for humans than its parent compound has been found up to approximately 12300 times higher levels than the EPA guidelines suggest (0.000086 microg/l). Both DCB and benzidine were found in the sediment phase. DCB was observed at almost 70 mg/kg in a sample collected in 1993. The concentrations in both phases have declined in recent years. To assess the threat of the released pollutants, it is necessary to understand how pollutants tend to behave in various media. Therefore, it is crucial to identify and quantify all sources of the chemical and its congeners in order to meaningfully predict the fate (and transport) of a hydrophobic organic compound (HOC) in the environment.     

Fresnel lens to concentrate solar energy for the photocatalytic decoloration and mineralization of orange II in aqueous solution

The decoloration and mineralization of the azo dye orange II under conditions of artificial ultraviolet light and solar energy concentrated by a Fresnel lens in the presence of hydrogen peroxide and TiO(2)-P25 was studied. A comparative study to demonstrate the viability of this solar installation was done to establish if the concentration reached in the focus of the Fresnel lens was enough to improve the photocatalytic degradation reaction. The degradation efficiency was higher when the photolysis was carried out under concentrated solar energy irradiation as compared to UV light source in the presence of an electron acceptor such us H(2)O(2) and the catalyst TiO(2). The effect of hydrogen peroxide, pH and catalyst concentration was also determined. The increase of H(2)O(2) concentration until a critical value (14.7 mM) increased both the solar and artificial UV oxidation reaction rate by generating hydroxyl radicals and inhibiting the (e(-)/h(+)) pair recombination, but the excess of hydrogen peroxide decreases the oxidation rate acting as a radical or hole scavenger and reacting with TiO(2) to form peroxo-compounds, contributing to the inhibition of the reaction. The use of the response surface methodology allowed to fit the optimal values of the parameters pH and catalyst concentration leading to the total solar degradation of orange II. The optimal pH range was 4.5-5.5 close to the zero point charge of TiO(2) depending on surface charge of catalyst and dye ionization state. Dosage of catalyst higher than 1.1 gl(-1) decreases the degradation efficiency due to a decrease of light penetration.     

Sorption and reduction of tetrachloroethylene with zero valent iron and amphiphilic molecules

Effects of surfactants and natural organic matter (NOM) on the sorption and reduction of tetrachloroethylene (PCE) with zero valent iron (ZVI) were examined in this study. PCE reduction by ZVI depended on the ionic type of the surfactants. The removal of PCE and production of TCE with non-ionic Triton X-100 and cationic hexadecyltrimethyl-ammonium (HDTMA) at one-half and two times the critical micelle concentration (CMC) were 1.2-1.8 times higher than without surfactants because of the enhanced PCE partitioning and surface concentration by the sorbed surfactants. When anionic sodium dodecyl benzene sulfonate (SDDBS) at one-half and two times CMC and NOM at 20 mg l(-1) and 50 mg l(-1) concentrations were used, the removal of PCE doubled and TCE production decreased. In the presence of SDDBS, TCE production by ZVI was lower than with HDTMA and Triton X-100 while PCE removal was higher than with the other surfactants.     

Fe(III)-oxalate complexes induced photooxidation of diethylstilbestrol in water

In this work, the photooxidation of diethylstilbestrol (DES), a synthetic estrogen, was investigated in a concentric reactor under a 125 W high-pressure mercury lamp (lambda > or = 365 nm). The photooxidation efficiencies were dependent on the pH values and Fe(III)/oxalate ratios of the system, with higher efficiency at pH 3.50+/-0.05 and Fe(III)/oxalate ratio 10.0/120.0 micromol l(-1). The photooxidation reactions obeyed the law of pseudo-first-order reaction at the concentration over the range of 2.0-10.0 mg l(-1) of DES. The photooxidation rates decreased with increasing the initial concentrations of DES. For 2.0 mg l(-1) DES, the observed photooxidation rate coefficient (k(obs)) was 0.00622 min(-1). By using GC-MS and LC-MS techniques, the predominant photooxidation products DES-o-catechol ([M](+), m/z 284) and DES-4-semiquinone ([M](-), m/z 267) were respectively identified and the mechanisms for the oxidative degradation were proposed. When DES reacted with OH radicals, C atoms in 3-position were added with OH radicals to produce hydrolyzed DES radical followed by two oxidation pathways: (1) dehydrolyzing to produce DES-4-semiquinone which was oxidized further to DES-4,4'-quinone; (2) undergoing peroxidation by O(2) and getting rid of HO(2) radical to produce DES-o-catechol. After that, the two H atoms on the hydroxy group of the catechol were extracted in two individual steps to form intermediates semiquinone radical and o-quinone. The catechol intermediates underwent further oxidation, benzene ring cleavage and decarboxylation, up to mineralization ultimately.     

膜基活化溶液中活化剂在回收温室气体CO2过程中的作用

将AMP和PZ作为活化剂添加于MDEA溶液中,形成活化溶液,研究了膜基活化溶液回收温室气体CO₂性能,着重考察活化剂的活化作用和对膜接触器传质加强的影响,提出一个活化机理来解释活化现象,建立了阻力层方程模型, 并模拟膜基活化溶液回收CO₂的传质过程。结果表明,活化剂对膜接触器传质的加强起到重要作用,具有双氨基环状结构的PZ对传质的加强作用高于具有空间位阻结构的AMP;活化溶液的CO2回收率和传质通量明显高于未活化的MDEA溶液,活化性能PZ＞AMP;活化剂的活化效应与分子结构有关;流体力学的改变对传质的影响有限,活化剂的反应动力学对传质的加强起主导作用;阻力层方程模型能较好地模拟膜基活化溶液回收CO₂传质过程,传质通量和总传质系数的模型值与实验值符合较好。     

The two-phase leaching of Pb, Zn and Cd contaminated soil using EDTA and electrochemical treatment of the washing solution

The feasibility of a novel two-phase method for remediation of Pb (1374 mg kg(-1)), Zn (1007 mg kg(-1)), and Cd (9.1 mg kg(-1)) contaminated soil was evaluated. In the first phase we used EDTA for leaching heavy metals from the soil. In the second phase we used an electrochemical advanced oxidation process (EAOP) for the treatment and reuse of washing solution for soil rinsing (removal of the soil-retained, chelant-mobilized metallic species). In EAOP, a boron-doped diamond anode was used for the generation of hydroxyl radicals and oxidative decomposition of EDTA-metal complexes at a constant current density (15 mA cm(-2)). The released metals were removed from the solution by filtration as insoluble participate and by electro-deposition on the cathode. Four consecutive additions of 5.0 mm ol kg(-1) EDTA (total 20 mmol kg(-1)) removed 44% Pb, 14% Zn and 35% Cd from the soil. The mobility of the Pb, Zn and Cd (Toxicity Characteristic Leaching Procedure) left in the soil after remediation was reduced by 1.6, 3.4 and 1.5 times, respectively. The Pb oral availability (Physiologically Based Extraction Test) in the simulated stomach phase was reduced by 2.4 and in the intestinal phase by 1.7 times. The discharge solution was clear, almost colorless, with pH 7.73 and 0.47 mg L(-1) Pb, 1.03 mg L(-1) Zn, bellow the limits of quantification of Cd and 0.023 mM EDTA. The novel method enables soil leaching with small water requirements and no wastewater generation or other emissions into the environment.     

Removal of selected endocrine disrupting chemicals and personal care products in surface waters and secondary wastewater by ozonation

This study investigated the removal of parabens, N,N-diethyl-m-toluamide (DEET), and phthalates by ozonation. The second-order rate constants for the reaction between selected compounds with ozone at pH 7 were of (2.2 +/-0.2) X 10(6) to (2.9 +/-0.3) X 10(6) M 1/s for parabens, (2.1+/- 0.3) to (3.9 +/-0.5) M-1/s for phthalates, and (5.2 +/-0.3) M-1/s for DEET. The rate constants for the reaction between selected compounds with hydroxyl radical ranged from (2.49 +/-0.06) x 10(9) to (8.5 +/-0.2) x 10(9) M-1/s. Ozonation of selected compounds in secondary wastewater and surface waters revealed that ozone dose of 1 and 3 mg/L yielded greater than 99% depletion of parabens and greater than 92% DEET and phthalates, respectively. In addition, parabens were found to transform almost exclusively through the reaction with ozone, while DEET and phthalates were transformed almost entirely by hydroxyl radicals (.OH).     

Comparison of bio-dissolution of spent Ni-Cd batteries by sewage sludge using ferrous ions and elemental sulfur as substrate

Bioleaching of spent Ni-Cd batteries using acidified sewage sludge was carried out in a continuous flow two-step leaching system including an acidifying reactor and a leaching reactor. Two systems operated about 30d to achieve almost complete dissolution of heavy metals Ni, Cd and Co in four Ni-Cd batteries. Ferrous sulphate and elemental sulfur were used as two different substrates to culture indigenous thiobacilli in sewage sludge. pH and ORP of the acidifying reactor was stabilized around 2.3 and 334mV for the iron-oxidizing system and 1.2 and 390mV for the sulfur-oxidizing system. It was opposite to the acidifying reactor, the pH/ORP in the leaching reactor of the iron-oxidizing system was relatively lower/higher than that of the sulphur-oxidizing system in the first 17d. The metal dissolution, in the first 12-16d, was faster in the iron-oxidizing system than in the sulphur-oxidizing system due to the lower pH. In the iron-oxidizing system, the maximum solubilization of cadmium (2500mg l(-1)) and cobalt (260mg l(-1)) can be reached at day 6-8 and the most of metal nickel was leached in the first 16d. But in the sulphur-oxidizing system there was a lag period of 4-8d to reach the maximum solubilization of cadmium and cobalt. The maximum dissolution of nickel hydroxide (1400mg l(-1)) and metallic nickel (2300mg l(-1)) occurred at about day 12 and day 20, respectively.     

Influence of the colloid type on the transfer of 60Co and 85Sr in silica sand column under varying physicochemical conditions

The influence of two types of colloids (natural organic matter, NOM), a colloid with high affinity for radionuclides (RN(s)), and hydrophilic synthetic latex (SHL), a colloid with low affinity for RN(s) on the transfer of (60)Co and (85)Sr in a silica sand column was studied under different physicochemical conditions: pH (4.9), ionic strength (10(-3) M and 10(-2) M), concentration of colloids (100 mg l(-1), 10 mg l(-1)), flow velocity (12.4 cm h(-1) and 3.7 cm h(-1)), water saturation of the column (100% and 70%). In the absence of colloids, the transfer of (60)Co and (85)Sr was retarded compared to the transfer of the conservative tracer. In the presence of colloids and according to the specific physicochemical conditions, an acceleration or retardation of (60)Co and (85)Sr transfer was observed compared to their transfer in the absence of colloids. Our results evidenced that any colloids even with low reactivity could significantly modify the RN transfer. However, the extent to which the transfer was influenced differs according to the colloid type; the NOM exhibiting higher impact than SHL. Batch experiments helped in interpreting of the interactions between the colloids, RN(s) and solid phase observed in column.     

Decolorization and degradation of H-acid and other dyes using ferrous-hydrogen peroxide system

In this study, advanced oxidation process utilizing Fenton's reaction was investigated for the decolorization and degradation of two commercial dyes viz., Red M5B, Blue MR and H-acid, a dye intermediate used in chemical industries for the synthesis of direct, reactive and azo dyes. Effect of Fe2 +, H2O2, pH, and contact time on the degradation of the dyes was studied. Maximum color and COD removal was obtained for Red MSB, H-acid and Blue MR at 10-25 mg/l of Fe2+ dose and 400-500 mg/l of H2O2 dose at pH 3.0. The initial oxidation reaction was found to fit into first order rate kinetics and the rate of oxidation of H-acid was higher than the other dyes. Release of chloride and sulfate from the Fenton's treated Red M5B dye and sulfate from H-acid and Blue MR indicates that the dye degradation proceeds through cleavage of the substituent group.     

Effect of manganese ion on the mineralization of 2,4-dichlorophenol by ozone

Mineralization of 2,4-dichlorophenol (DCP) was studied by ozone with Mn(2+) as an ozonation catalyst. Laboratory scale semi-batch ozonation experiments were conducted at room temperature. The results showed that trace amount of Mn(2+) accelerated the mineralization of DCP. Total organic carbon removal rate was independent on Mn(2+) dosage at its range of 0.1-0.5 mgL(-1). Dissolved ozone concentration in the solution remained low level in the catalytic ozonation process, which indicated that Mn(2+) catalyzed decomposition of ozone. DCP mineralization was inhibited in catalytic ozonation by the addition of carbonate. Electron spin resonance/spin-trapping technique was used to determine hydroxyl radicals, and the results showed that larger amounts of hydroxyl radicals were produced in catalytic ozonation system than those of single ozonation. Intermediates mainly including aliphatic carboxylic acids were determined qualitatively and semi-quantitatively by GC-MS. And, a general pathway for mineralization of DCP was proposed.