Nitrate removal from water using UV-M/S2O4 2− advanced reduction process

In this work, a new process called advanced reduction process (ARP) was used for nitrate removal from water. This ARP process combines sodium dithionite as reducing agent with ultraviolet irradiation using medium pressure lamps (UV-M) as an activating method. Experimental results showed that UV-M/S₂O₄ ^2? process achieved almost complete removal of nitrate from aqueous solutions containing 25 mg NO₃ ^?/L using stoichiometric dose of dithionite of 68.8 mg/L at neutral pH conditions. Analysis of final products and material balance confirmed that NO₃ ^? ions were reduced to ammonium with formation of nitrite as intermediates in addition to the formation of small amounts of volatile species, mainly ammonia and nitrogen gas. Effects of certain experimental parameters including dithionite dose, initial pH, initial nitrate concentration, and UV light source on the kinetics and efficiency of nitrate reduction were evaluated. Increasing dithionite dose augmented the rate of nitrate reduction and enhanced the efficiency of ARP process. Dithionite doses higher than stoichiometric ratios led to complete removal of nitrate in shorter reaction time. UV-M/S₂O₄ ^2? process was found to be effective only under neutral pH or alkaline conditions, and its removal efficiency is negligible in acidic medium (pH < 4). Irradiation with UV-M was more effective than low pressure or narrow band lamps. These results can be attributed to the contribution of several mechanisms for nitrate reduction to ammonium. These include the following: direct photolysis, chemical reduction of nitrate dithionite, and mediated reduction of nitrate by free reducing radicals.     

Reductive dechlorination of polychlorinated biphenyls (PCBs) by ultrasound-assisted chemical process (UACP)

The dechlorination of aqueous polychlorinated biphenyls (PCBs) using the ultrasound-assisted chemical process (UACP), which is a combination of ultrasonic irradiation and radical generations using di-tert-butyl peroxide as a radical initiator and ferrous ion as a catalyst at moderate temperature in alkaline 2-propanol, was demonstrated with a high reduction of PCBs. A commercial PCB-containing compound, Aroclor 1260, was also decomposed with the removal efficiency of 97 % achieved within 3 h of UACP. The gas chromatograph was used as a quantitative method to measure the decomposition rate of PCBs. The competitive elimination among the ortho (2-position), meta (3-position), and para (4-position) chlorine atoms of PCB was also identified.     

Oxidation of bisphenol A by a boron-doped diamond electrode in different water matrices: transformation products and inorganic by-products

An electrochemical advanced oxidation process employing a boron-doped diamond anode for the treatment of synthetic waters and secondary effluents of wastewater treatment plants (WWTP) was studied. The efficiency and formation of transformation products (TPs) for this treatment process were investigated at different current densities for bisphenol A (BPA) spiked to synthetic water and WWTP effluents. A complete removal of the parent compound was achieved in WWTP effluents. Higher applied current densities resulted in faster removal. At the same time, a correlation between the applied current density and the ozone concentration measured in the bulk solution was revealed. Hence, the observed transformation of BPA is likely due to the generation of reactive oxygen species such as hydroxyl radicals and ozone. Based on a suspected target screening approach, four known TPs and two unreported (new) TPs were identified by LC–MS analysis. These results suggest a transformation pathway following three steps: hydroxylation of the aromatic ring, followed by oxidation of the isopropylidene bridge and finally a ring opening and formation of organic acids and other small molecules. The presence of chloride ions in WWTP effluents can result in the generation of excessive concentrations of chlorate and perchlorate during electrochemical oxidation. Applying a current density of 208 mA cm^?2, a complete elimination of BPA was achievable after 15 min (Q/V = 430 mA h L^?1); however, the oxidation resulted in concentrations of chlorate and perchlorate of 2.85 and 5.65 mg L^?1, respectively. These values were directly dependent on the exposure time and desired degree of BPA removal.     

Effect of extracellular polymeric substances on sludge reduction potential of Bacillus licheniformis

The disposal of wastewater sludge generated during the treatment of the various municipal and industrial wastewaters is a major environmental problem. In this study the thermophilic bacterium Bacillus licheniformis, which enhances the efficiency of sludge reduction, was isolated from waste activated sludge acclimated to 55 °C. The resulting suspended solids’ degradation was 12 % and chemical oxygen demand solubilization was 18 %. To further enhance the sludge reduction potential, extra polymeric substances, which play a major role in the formation of flocs, were removed. A chemical extractant, ethylenediaminetetraacetate that is also a cation binding agent, was used to remove the extra polymeric substances. After the removal of extra polymeric substances, the suspended solids’ degradation increased from 12 to 23 % and the chemical oxygen demand solubilization increased from 18 to 25 %. These observations confirm that Bacillus licheniformis enhanced sludge reduction in non-flocculated sludge (with the removal of extra polymeric substances) as compared to flocculated sludge (without the removal of extra polymeric substances).     

紫外/氯工艺对水中微囊藻毒素的去除

水体富营养化导致藻类的爆发进而引起藻毒素的释放。微囊藻毒素(MCLR)是最为常见的藻毒素,具有很强的毒性,对人类健康具有潜在危害。本文采用紫外/氯组合工艺,研究其对水中微囊藻毒素的控制效果。结果表明：紫外/氯共同作用下能够产生·Cl、·OH等活性自由基,具有协同降解MCLR的作用,30 min即可实现MCLR的完全去除,其降解效率随着氯投加质量浓度的增加而升高。在酸性及中性条件下,pH的变化对紫外/氯降解MCLR没有影响;在碱性条件下,MCLR的降解效率随pH的升高显著降低,pH升高至9时,30 min MCLR的降解效率仅为41.3%。此外,不同的水样来源和水质特点对紫外/氯联合降解MCLR的效率具有显著影响,纯水、西湖水及水厂滤后水的30 min去除率分别为99.5%,40.2%及63.3%。MCLR 的降解效率随腐殖酸质量浓度增大而降低,在60 min作用时间内,不含腐殖酸水样的MCLR去除率高达99.5%,当腐殖酸质量浓度增加到10 mg/L时,MCLR去除率仅为45.3%。     

Degradation of β-blockers in water by sulfate radical-based oxidation: kinetics,mechanism and ecotoxicity assessment

This study investigated the kinetics and degradation pathway of acebutolol, metoprolol and sotalol in a sulfate radical-based advanced oxidation process. The selected pharmaceuticals were β-blockers which have been used to treat cardiovascular diseases. Due to its frequent use, the presence of these pharmaceuticals in the environment has been regularly reported. In this study, sulfate radicals were generated using peroxymonosulfate with cobalt (II) as activator. At pH 7 and 25 °C, the second-order rate constant for the reaction between SO₄ ^·? with metoprolol, acebutolol and sotalol was (1.0 ± 0.1) × 10¹⁰, (2.0 ± 0.1) × 10¹⁰ and (3.0 ± 0.2) × 10¹⁰ M^?1 s^?1, respectively. Sixteen transformation by-products were identified from the selected β-blockers. These transformation by-products were mainly formed through the hydroxylation, aromatic ring-opening reaction and aliphatic chain oxidation. The decomposition of β-blockers by sulfate radicals was found to start from the formation of hydroxylated β-blockers followed by an aromatic ring-opening reaction. In general, this study showed that β-blockers reacted favorably with sulfate radicals, and various transformation by-products could be produced. The result from the ecotoxicity assessment showed that almost all of the transformation by-products were less toxic than its parent compound. Therefore, a sulfate radical-based advanced oxidation process could be an effective method for the treatment of β-blockers in water.     

Visible light N-TiO<Subscript>2</Subscript>-induced photodegradation of Congo red: characterization,kinetics and mechanistic study

In this study, the photocatalytic degradation of Congo red has been investigated in N-doped TiO₂ (N-TiO₂) aqueous suspensions under visible light irradiation. Visible light-active N-TiO₂ was successfully prepared at three different weight contents (2.5, 5, and 7%) employing sol–gel method. It was able to harvest the visible irradiation with wavelength suitable for activation. X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectrometer, diffused reflectance UV–Vis spectroscopy, nitrogen adsorption Brunauer–Emmert–Teller, Raman spectroscopy, photoluminescence and X-ray photoelectron spectrometer were used to characterize the doped catalyst. The samples had a relatively large specific Brunauer–Emmert–Teller surface areas of about 42 m² g^?1 with average X-ray diffraction crystalline size of 52 nm and showed visible light photocatalytic activity at about 408 nm. The impacts of several operating parameters on the Congo red photodegradation process were examined. Langmuir–Hinshelwood model exhibited pseudo-first-order degradation kinetics. N-TiO₂-assisted plausible photodegradation mechanism has been suggested based on the qualitatively detected intermediate compounds.     

Effects of sludge pretreatment on sludge reduction in a lab-scale anaerobic/anoxic/oxic system treating domestic wastewater

Excess sludge disposal is one of the serious challenges in biological wastewater treatment. Reduction of sludge production would be an ideal way to solve sludge-associated problems rather than the post-treatment of the sludge produced. In this study, a new wastewater treatment process combining anaerobic/anoxic/oxic system with thermochemical sludge pretreatment was tested in a laboratory scale experiment. In this study, the effects of the sludge pretreatment on the excess sludge production in anaerobic/anoxic/oxic were investigated. The system was operated in two Runs (1 and 2). In Run 1, the system was operated as a reference and in Run 2, a part of the mixed liquid was pretreated thermochemically and was returned to the bioreactor. The average solubilization efficiency of pretreated sludge was found to be about 35 % during the study period of 220 days. Sludge production rate in Run 2 was less than that in Run 1 by about 52 %. Total phosphorous was removed by enhanced biological phosphorous removal with the removal efficiency of 83–87 % and 81–83 % for Run 1 and Run 2, respectively. Total nitrogen removal in Run 2 (79–82 %) was slightly higher than that in Run 1 (68–75 %). The mixed liquor suspended solids/mixed liquor volatile suspended solids ratio was identical after both runs in the range 78–83 %. The effluent water qualities were not significantly affected when operated with thermochemical pretreatment at pH 11 and 60 °C for 3 h during 7 months. From the present study it is concluded that thermochemical sludge pretreatment of anaerobic/anoxic/oxic process plays an important role in reduction of sludge production.     

Treatment of an ECF bleaching effluent with white-rot fungi in an air-lift bioreactor

Pulp and paper mills utilise huge amount of natural resources, inorganic and organic materials along with large volume of water in different stages of paper manufacturing, resulting in a significant volume of effluents. The aim of this work was to investigate the treatment of a bleaching effluent [effluent chlorine free (ECF)] from the cellulose industry with white-rot fungi in an air-lift bioreactor. This effluent was submitted to the biological treatment with three white-rot fungi, and, every 24 h for 120 h, analytical tests were performed to analyse the quality parameters of treatment (COD, phenols, colour, pH). Before and after treatment, the effluent was analysed as its molecular mass distribution and absorptivity in the UV/VIS. Lentinus edodes, Trametes versicolor and Trametes villosa promoted similarly significant reductions in the following characteristics: (a) effluent colour (40–44 %), (b) total phenol (30–51 %) and (c) COD (37–43 %). The UV/visible spectrometry reading of the effluent after the fungi treatment showed a reduction in the absorbance of all wavelengths between 260 and 500 nm. The size exclusion HPLC profile of the effluent was modified, and the treatment promoted changes in the intensity of the peaks associated with compounds of high and low molecular weight. Phenoloxidases were produced during the treatment. T. versicolor produced the highest levels of laccase, and L. edodes was the only fungus that produced peroxidases.     

Photocatalytic degradation of azo dye Orange II in aqueous solutions using copper-impregnated titania

During dyeing process, industries consume large quantity of water and subsequently produce large volume of wastewater. This wastewater is rich in color and contains different dyes. Orange II is one of them. In this article, metal-impregnated TiO₂ P-25 catalyst was used to enhance the photocatalytic degradation of Orange II dye. Photodegradation percentage was followed spectrophotometrically by the measurements of absorbance at λ _max = 483 nm. The effect of copper-impregnated TiO₂ P-25 photocatalyst for the degradation of Orange II has been investigated in terms of percentage removal of color, chemical oxygen demand (COD) and total organic carbon (TOC). As such 98 % color removal efficiency, 97 % percentage removal of COD and 89 % percentage removal of TOC was achieved with TiO₂ P-25/Cu catalysts under typical conditions. Copper-impregnated TiO₂ P-25 photocatalyst showed comparatively higher activity than UV/H₂O₂ homogeneous photodegradation. The relative electrical energy consumption for photocatalytic degradation was considerably lower with TiO₂ P-25/Cu photocatalyst than that with homogeneous photodegradation. Transmission electron microscopic analysis was used for catalyst characterization.     

Novel preparation of sensitized ZnS nanoparticles and its use in photocatalytic degradation of tetracycline

Sensitized ZnS nanoparticles were synthesized by chemical precipitation method using anthocyanin as the capping agent and sensitizer. X-ray diffractometer, field-emission scanning electron microscope, transmission electron microscopy, UV visible spectrophotometer, Fourier transform infrared spectroscopy and photoluminescence spectrometry methods were used for the characterization of nanoparticles. The electron microscopy studies of nanoparticles showed that the size of crystallites is in the range of 35–80 nm and optical studies showed a blue shift in the absorption edge by adding capping agent. The effective band gap energy was increased with decrease in the particle size. Photocatalytic activities of sensitized ZnS and pure ZnS were evaluated by degradation of tetracycline in aqueous solution under visible light irradiation, and progress of the reaction was monitored spectrophotometrically. The different parameters affecting degradation such as the pH of solution, amount of semiconductor and reusability of catalyst for three cycles and the photocatalytic degradation kinetics of tetracycline were studied. More than 80% degradation was achieved within 5 h under visible light.     

Biogenic silver nanoparticles on carbonaceous material from sewage sludge for degradation of methylene blue in aqueous solution

Silver nanoparticles (Ag NPs) were synthesized in situ, using a one-step green methodology with Camellia sinensis (green tea) aqueous extract as reducing agent, and supported on a carbonaceous material (Ag-CM), originated from the pyrolysis of sewage sludge. UV–Vis spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and Brunauer–Emmet–Teller were used to characterize the nanocomposite. Ag-CM composite exhibited very good catalytic activity in the degradation process of methylene blue (MB) dye in aqueous solution without using sunlight or UV radiation. Batch kinetic and isothermal experiments, using 30 mg/L MB solution, showed that Ag-CM composite removed near to 91 % of MB in 9 h, whereas the carbonaceous material alone removed only 60 % in 30 h. Experimental data were adjusted to different kinetic and isotherms models, where both materials fit the second-order and Langmuir–Freundlich models, respectively; therefore, a chemisorption mechanism probably occurs in these heterogeneous materials.     

Removal of acetaminophen from hospital wastewater using electro-Fenton process

The current work deals with efficient removal of acetaminophen (AC) from hospital wastewater using electro-Fenton (EF) process. The degradation yield of 99.5% was obtained under optimal experimental conditions, namely 5.75 mg L^?1 initial AC concentration, 2.75 pH solution, 3-cm inter-electrode distance, 100 mg L^?1 KCl electrolyte, 122.5 µL L^?1 H₂O₂, 8 mA cm^?2 current density at equilibrium time of 8 min. Analysis of variance (ANOVA) suggested that the effect of mentioned operating parameters was statistically significant on the AC removal. The low probability amount of P value (P < 0.0001), the Fisher’s F-value of 65.91, and correlation coefficient of the model (R² = 0.9545) revealed a satisfactory correlation between the experimental and the predicted values of AC removal. The predicted removal efficiency of 99.4% was in satisfactory agreement with the obtained experimental removal efficiency of 98.7%. The AC degradation during the EF followed a first-order kinetic model with rate constants (K_app) of 0.6718 min^?1. Using the ordinary radical scavengers revealed that main mechanism of AC degradation controlled by the hydroxyl free radicals produced throughout the EF process. The excess amount of iron (II) scavenged the active radicals and diminished the concentration of ^·OH available to react with AC. The optimum molar ratio of H₂O₂ to Fe²⁺ was found to be 2.5. The developed EF process as a promising technique applied for treatment of real samples.     

Control of the biofouling bryozoan, Plumatella repens, using pulsed chlorine treatment

Bryozoans are common biofoulers of under-drain filter nozzles in rapid gravity filters in water treatment works. A potential method for controlling bryozoan biofouling is the use of chlorine in backwash water. Repeatedly exposing bryozoan colonies with chlorine for 20 min every 24 h in an experimental setting, to replicate what would occur if the backwash was chlorinated, caused significant reduction in colony growth and size. After 10 days repeated treatment in good conditions for bryozoan propagation, the EC₅₀ (the chlorine concentration required to decrease growth such that treated colonies were half the size of control colonies) was 1.6 ppm (SE 0.3). In sub-optimal conditions for propagation, the impact of chlorine was greater. The majority of colonies treated with 1 ppm and above did not grow or even decreased in size over 5 days. However, a chlorine concentration of 5 ppm was necessary, even in sub-optimal conditions, to ensure all colonies decreased in size over 5 days of treatment; this is too high to be acceptable to water companies due to the risk of carcinogenic by-products. Nevertheless, the observed decline in feeding activity of bryozoans exposed to chlorine levels >1 ppm suggests that repeated backwashing with chlorine may cause colony death over time, especially in sub-optimal conditions. Chlorine backwashes may therefore be an effective long-term control strategy, especially in locations such as rapid gravity filters where it is suggested that upstream processes are likely to create sub-optimal conditions for bryozoan growth.     

Mineralization of organic matter from vinasse using physicochemical treatment coupled with Fe<Superscript>2+</Superscript>-activated persulfate and peroxymonosulfate oxidation

Application of advanced oxidation process for wastewater treatment has gained more attention recently. In this study, the efficiency of coagulation–flocculation pretreatment coupled with sulfate radical-based advanced oxidation process (SR-AOP) in the removal and mineralization of organic matter of sugarcane vinasse was evaluated. For coagulation–flocculation, jar-test experiment was carried out with ferric chloride as coagulant and the removal of TOC, color and UV₂₅₄ was determined. The results revealed that by using 15 g/L of coagulant, 70 % of TOC removal and nearly 100 % of UV₂₅₄ and color removal were achieved. The pretreated vinasse was then subjected to SR-AOP. In this study, sulfate radical was generated using persulfate (PS) and peroxymonosulfate (PMS) activated by Fe(II). The effect of reaction time, oxidants to Fe(II) ratio and pH on the TOC removal efficiency were investigated. For the effect of reaction time, the TOC removal was found to increase significantly for the first 5 min. TOC removal was found to increase with increasing concentration of Fe(II) for PMS. However, for Fe(II)/PS, the TOC removal efficiency was decreased with increasing Fe(II) concentration. Both Fe(II)/PMS and Fe(II)/PS showed the highest TOC removal efficiency when the oxidation was carried out at pH 7. By using the selected optimum condition, nearly 70 and 49 % of TOC removal were achieved for PMS/Fe(II) and PS/Fe(II), respectively. Therefore, it can be concluded that SR-AOP can be a promising alternative method for TOC removal from sugarcane vinasse.     

Aquifer heat storage: sulphate reduction with acetate at increased temperatures

Aquifer thermal energy storage in urban and industrial areas can lead to an increase in subsurface temperature to 70 °C and more. Besides its impacts on mineral and sorption equilibria and chemical reaction kinetics in an aquifer, temperature sensitively influences microbial activity and thus redox processes, such as sulphate reduction. Microorganism species can only operate within limited temperature ranges and their adaptability to temperature is a crucial point for the assessment of the environmental consequences of subsurface heat storage. Column experiments with aquifer sediment and tap water at 10, 25, 40, and 70 °C showed that under the constant addition of acetate sulphate reduction could be initiated after 26–63 pore volumes exchanged at all temperatures. Fastest initiation of sulphate reduction with the highest reduction rates was found at 40 °C. Maximum rate constants during experimental run-time were 0.56 h^?1 at 40 °C and 0.33, 0.36, and 0.25 h^?1 at 10 and, 25, and 70 °C, respectively. Hence, microbial activity was enhanced by a temperature increase to 40 °C but was significantly lowered at 70 °C. At 25 °C methane was found in solution, indicating the presence of fermenting organisms; at 10, 40, and 70 °C no methane production was observed. It could be shown that redox processes in an aquifer generally can adapt to temperatures significantly higher than in situ temperature and that the efficiency of the reduction process can be enhanced by temperature increase to a certain limit. Enhancement of sulphate reduction in an aquifer due to temperature increase could also allow enhanced degradation of organic ground water contaminants such as BTEX, where sulphate is an important electron acceptor.     

Enhanced bioremoval of refractory compounds from dyeing wastewater using optimized sequential anaerobic/aerobic process

The upflow anaerobic sludge blanket process followed by the biological aerated filter process was employed to improve the removal of color and recalcitrant compounds from real dyeing wastewater. The highest removal efficiency for color was observed in the anaerobic process, at 8-h hydraulic retention time, seeded with the sludge granule. In the subsequent aerobic process packed with the microbe-immobilized polyethylene glycol media, the removal efficiency for chemical oxygen demand increased significantly to 75 %, regardless of the empty bed contact time. The average influent non-biodegradable soluble chemical oxygen demand was 517 mg/L, and the average concentration in effluent from the anaerobic reactor was 363 mg/L, suggesting the removal of some recalcitrant matters together with the degradable ones. The average non-biodegradable soluble chemical oxygen demand in effluent from the aerobic reactor was 87, 93, and 118 mg/L, with the removal efficiency of 76, 74, and 67 %, at 24-, 12-, and 8-h empty bed contact time, respectively. The combined anaerobic sludge blanket and aerobic cell-entrapped process was effective to remove the refractory compounds from real dyeing wastewater as well as in reducing organic loading to meet the effluent discharge limits. This integrated process is considered an effective and economical treatment technology for dyeing wastewater.     

Immobilization of copper under an acid leach of colloidal pyrite waste rocks by a fixed-bed column

Colloidal pyrite waste rocks (CPWR) which are mainly composed of colloidal pyrite and siderite widely deposit in sulfide mines in the middle and lower reaches of the Yangtze River belt, China, especially in Tongling City, Anhui Province, China. In this paper, a fixed-bed column was used to investigate the weathering and oxidation of CPWR and its role in immobilizing low-concentration Cu (10 mg L^?1) under weakly acidic leach (pH = 5.0). The experimental results indicated that the breakthrough capacity was around 14.0 mg Cu g^?1 CPWR when Cu²⁺ breakthrough concentration was 0.5 mg L^?1. Sequential extraction of Cu and dithionite–citrate–bicarbonate extraction of free iron in the used CPWR after the column breakthrough indicated that Cu removal by CPWR consisted of the following processes: oxidation of pyrite and dissolution of siderite in CPWR, ferrous oxidation, and adsorption of Cu on ferric (hydr)oxides. This study shows the potential application of CPWR as an effective sorbent for the removal of low-concentration Cu from acid mine drainage.     

Preparation of magnetic microgels for catalytic reduction of 4-nitrophenol and removal of methylene blue from aqueous medium

This work describes the synthesis of poly(acrylic acid) microgels and fabrication of magnetic cobalt nanoparticles in the prepared microgels. Cobalt nanoparticles were fabricated by loading the cobalt (II) ions in microgels from aqueous solution and their subsequent reduction with sodium borohydride (NaBH₄). Bare and composite microgels were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. The catalytic properties of the prepared microgel composites were investigated by using them as catalyst for the reduction of 4-nitrophenol and methylene blue. The effect of temperature and catalyst dose on the rate of reduction of these toxic pollutants was investigated. The reusability of prepared catalysts was also studied for the five consecutive cycles, and an increase in catalytic activity was observed after every cycle. The prepared bare and magnetic microgels were found as very effective adsorbent for the removal of methylene blue from aqueous medium. Very rapid adsorption rate was found for the removal of methylene as its 100 mg was adsorbed on per gram of dried hydrogels in about 25 min. The effects of different parameters like amount of adsorbate and concentration of adsorbent on the adsorption process were studied. Langmuir, Freundlich and Temkin adsorption isotherms were applied, and it was found that adsorption of MB follows Freundlich model better than others. Furthermore, pseudo-first-order and pseudo-second-order kinetic models were also applied and adsorption of MB was found to abide by pseudo-second-order kinetics.