Degradation of azo dye by an UV/H2O2 advanced oxidation process using an amalgam lamp

The discharge of dyes into water is an ecological problem that can be alleviated by advanced oxidation processes (AOPs), such as UV/H₂O₂ treatments. Searching for more efficient light sources is a way to improve AOPs’ efficiency. This work tested the efficiency of an amalgam lamp on the degradation of an azo dye, studying the effect of dye and H₂O₂ concentrations and pH, and the influence of some salts on the decolouration rate of methyl orange. Actinometry showed that the amalgam lamp system was able to provide a high incident photon irradiance (6.30·10^?5 mol/cm² s). The amalgam lamp‐driven AOP was able to decolourize the dye at pseudo‐first‐order rates of 0.654–4.008 1/min, with increasing rates at low dye concentration and low pH and at high H₂O₂ concentrations until a maximum value is reached. The results show that the amalgam lamp can be an alternative light source for fast dye degradation by AOPs.     

O3/H2O2联合氧化法预处理制药废水的初步探讨

针对制药废水的特点和目前制药废水预处理技术现状,介绍了O3/H2O2在制药废水处理中的应用,阐述了O3/H2O2氧化工艺机理,分析了O3/H2O2联合氧化法在工程实际中的应用情况,并通过与其他方法对比,得出该工艺是最好的制药废水预处理工艺。     

高级氧化+SBR工艺处理聚乙二醇废水试验研究

研究了高级氧化+SBR组合工艺处理高浓度聚乙二醇(PEG)废水的效果及其影响因素。结果表明,采用芬顿试剂作为高级氧化剂,当FeSO4.7H2O投加量为800 mg/L,H2O2投加量为30 mL/L,反应时间为3.5 h时,CODCr去除率可达到50.5%;生化处理阶段所需采用两级SBR工艺,污泥浓度均为4 000 mg/L,一、二级厌氧及好氧反应时间分别为12和10 h;芬顿试剂氧化和厌氧处理对提高PEG废水的可生化性有明显效果;该组合工艺的出水水质可以达到《污水综合排放标准》(GB 8978—1996)中的二级排放标准。     

Paracetamol oxidation from aqueous solutions by means of ozonation and H2O2/UV system

Paracetamol oxidation from aqueous solutions is studied by means of ozonation and H(2)O(2) photolysis. Both oxidative systems are able to destroy the aromatic ring of the substrate with a partial conversion of the initial carbon content into carbon dioxide. For the adopted experimental conditions mineralization degrees up to 30% and 40% are observed with ozonation and H(2)O(2) photolysis, respectively. Main reaction intermediates and products are identified for both systems by HPLC and GC-MS analyses and a kinetic characterization is achieved.     

Application of ferrous-hydrogen peroxide for the treatment of H-acid manufacturing process wastewater

1-Amino-8-naphthol-3,6-disulfonic acid (H-acid) is widely used in chemical industries for synthesis of direct, acid, reactive and azoic dye. The wastewater from H-acid manufacturing process is rich in various substituted derivatives of naphthalene and is one of the most hardly-treated wastewaters. A pretreatment method, ferrous ion-peroxide oxidation combined with coagulation, has been studied. The results have shown that the optimum pH value is below 4 and the suitable ferrous ion dosage is 200 mg/l. The COD removal of H-acid wastewater is about 50% and the residue have proved biodegradable when hydrogen peroxide dosage is 30 g/l. Ferrous ion-peroxide oxidation process can also improve efficiency of coagulation treatment. The overall COD removal can reach 90% or more when the concentration of ferrous ion is 200 mg/l, the dosage of hydrogen peroxide is 3 g/l and the ferric chloride dosage of two stage coagulation treatment is 15 g/l and 5 g/l, respectively. The groups on naphthalene ring, such as − + NO₂, SO⁻₃ etc., are substituted by hydroxyl free radical, and then the ring is broken down during oxidation process of H-acid.     

Evaluation of UV/H2O2 treatment for the oxidation of pharmaceuticals in wastewater

Advanced oxidation treatment using low pressure UV light coupled with hydrogen peroxide (UV/H₂O₂) was evaluated for the oxidation of six pharmaceuticals in three wastewater effluents. The removal of these six pharmaceuticals (meprobamate, carbamazepine, dilantin, atenolol, primidone and trimethoprim) varied between no observed removal and >90%. The role of the water quality (i.e., alkalinity, nitrite, and specifically effluent organic matter (EfOM)) on hydroxyl radical (OH) exposure was evaluated and used to explain the differences in pharmaceutical removal between the three wastewaters. Results indicated that the efficacy of UV/H₂O₂ treatment for the removal of pharmaceuticals from wastewater was a function of not only the concentration of EfOM but also its inherent reactivity towards OH. The removal of pharmaceuticals also correlated with reductions in ultraviolet absorbance at 254 nm (UV₂₅₄), which offers utilities a surrogate to assess pharmaceutical removal efficiency during UV/H₂O₂ treatment.     

Advanced oxidation of the pharmaceutical drug diclofenac with UV/H2O2 and ozone

Diclofenac, a widely used anti-inflammatory drug, has been found in many Sewage Treatment Plant effluents, rivers and lake waters, and has been reported to exhibit adverse effects on fish. Advanced oxidation processes, ozonation and H2O2/UV were investigated for its degradation in water. The kinetic of the degradation reaction and the nature of the intermediate products were still poorly defined. Under the conditions adopted in the present study, both ozonation and H2O2/UV systems proved to be effective in inducing diclofenac degradation, ensuring a complete conversion of the chlorine into chloride ions and degrees of mineralization of 32% for ozonation and 39% for H2O2/UV after a 90 min treatment. The reactions were found to follow similar, but not identical, reaction pathways leading to hydroxylated intermediates (e.g. 2-[(2,6-dichlorophenyl)amino]-5-hydroxyphenylacetic acid) and C-N cleavage products (notably 2,5-dihydroxyphenylacetic acid) through competitive routes. Subsequent oxidative ring cleavage leads to carboxylic acid fragments via classic degradation pathways. In the pH range 5.0-6.0 kinetic constants (1.76 x 10(4)-1.84 x 10(4) M(-1) s(-1)) were estimated for diclofenac ozonation.     

关于改良A~2/O工艺和氧化沟处理的比较

对城市污水处理厂的两种处理工艺——改良A2/O工艺和氧化沟处理工艺作了介绍,在相同规模、相同进出水水质条件下,将两种处理工艺进行了技术、经济比较,从而使设计人员能根据实际情况确定污水处理工艺。     

Comparison of the efficiency of *OH radical formation during ozonation and the advanced oxidation processes O3/H2O2 and UV/H2O2

Comparison of advanced oxidation processes (AOPs) can be difficult due to physical and chemical differences in the fundamental processes used to produce OH radicals. This study compares the ability of several AOPs, including ozone, ozone+H2O2, low pressure UV (LP)+H2O2, and medium pressure UV (MP)+H2O2 in terms of energy required to produce OH radicals. Bench scale OH radical formation data was generated for each AOP using para-chlorobenzoic acid (pCBA) as an OH radical probe compound in three waters, Lake Greifensee water, Lake Zurich water, and a simulated groundwater. Ozone-based AOPs were found to be more energy efficient than the UV/H2O2 process at all H2O2 levels, and the addition of H2O2 in equimolar concentration resulted in 35% greater energy consumption over the ozone only process. Interestingly, the relatively high UV/AOP operational costs were due almost exclusively to the cost of hydrogen peroxide while the UV portion of the UV/AOP process typically accounted for less than 10 percent of the UV/AOP cost and was always less than the ozone energy cost. As the *OH radical exposure increased, the energy gap between UV/H2O2 AOP and ozone processes decreased, becoming negligible in some water quality scenarios.     

Application of multi-wavelength fluorometry for monitoring wastewater treatment process dynamics

Much of the methodology employed for characterizing wastewater and in modeling wastewater treatment processes employs off-line analysis. Off-line analysis is time consuming and not ideally suited to developing process control strategies. Clearly a rapid, inexpensive and reliable method suitable for following organic consumption and biomass production on-line would be very useful. In this study multiple excitation—multiple emission fluorometry was examined as a method for monitoring wastewater treatment processes. Results were first obtained for defined protein solutions and activated sludge to identify characteristic excitation and emission wavelength pairs. These results were then used to develop a rapid off-line assay for measurement of synthetic feeds consisting of protein substrates for batch aerobic and anoxic wastewater treatment processes and for on-line monitoring of cellular metabolic states in an anoxic process. Step-wise multiple regression and principal component analysis were employed for data analysis. The former was used to determine the most informative excitation and emission wavelength pairs while the latter was applied to reduce fluorescent spectra dimensions. Analysis of the batch kinetics suggests that this approach is valid and revealed some dynamic features of protein utilization and biomass accumulation under aerobic and anoxic conditions. A correlation was developed between COD-removal rates and the fluorescence signals in the two processes using fluorescent emission spectra rather than single signals. The data suggests that this multiple excitation—multiple emission fluorometry may be a suitable method for following wastewater and activated sludge dynamics and could be used as the basis for the development of expert system based biosensors.     

Partial wet oxidation of p-coumaric acid: Oxidation intermediates, reaction pathways and implications for wastewater treatment

p-Coumaric acid is representative of the polyphenolic fraction typically found in olive oil processing and wine-distillery wastewaters. The batch oxidation of p-coumaric acid has been investigated using a high-pressure reactor at temperatures varying from 403 to 523 K and pressures from 3 to 7 MPa. Concentrations of reaction intermediates were determined as a function of oxidation time using High Performance Liquid Chromatography (HPLC) as the main analytical technique, and an oxidation mechanism for p-coumaric acid is suggested. The results are discussed with respect to developing an integrated chemical-biological treatment process for organic wastewater.     

The effect of UV/H2O2 treatment on biofilm formation potential

Greater Cincinnati Water Works (GCWW) evaluated the efficacy of ultraviolet light/hydrogen peroxide advanced oxidation (UV/H₂O₂) for reducing trace organic contaminants in natural water with varying water qualities. A year-long UV/H₂O₂ pilot study was conducted to examine a variety of seasonal and granular activated carbon (GAC) breakthrough conditions. The UV pilot-scale reactors were set to consistently achieve 80% atrazine degradation, allowing comparison of low pressure (LP) and medium pressure (MP) lamp technologies for by-product formation. Because hydroxyl radicals react non-selectively with organic compounds, unintended by-product formation occurred.Total assimilable organic carbon (AOC) concentration increased through the reactors from 14 to 33% on average, depending on water quality. Natural organic matter (NOM) contains the precursors for AOC production, so when post-GAC water (versus conventionally treated water) served as reactor influent, less AOC was produced. No appreciable difference in AOC concentration was observed between LP and MP UV reactors. The Spirillum strain NOX fraction of the AOC increased from 50 to 65% on average, depending on the quality of the water. The increase in this fraction of AOC occurred because oxidation of NOM yielded smaller more assimilable organic compounds such as organic acids that are necessary for NOX growth. The Pseudomonas fluorescens strain P17 AOC concentration increased only when conventionally treated plant water was used as pilot influent. This organism thrives in waters of differing organic energy sources, but does not thrive well in carboxylic acids alone. The CONV water had more overall TOC that could contribute to higher P17 AOC counts.Biofilm coupon studies indicated that biofilms with greater heterotrophic plate counts were observed in the granular activated carbon (GAC) effluent streams receiving UV/H₂O₂ pre-treatment. Biofilm coupon studies additionally indicated that the effluent stream of the GAC column proceeded by the MP reactor exhibited more viable biofilm than the other GAC effluent streams based on an ATP-bioluminescence method. The increased viability of the biofilm produced by the MP UV reactor is likely a result of the multiple UV wavelengths and higher energy input characteristic of this technology.     

Simultaneous degradation of disinfection byproducts and earthy-musty odorants by the UV/H2O2 advanced oxidation process

Advanced treatment technologies that control multiple contaminants are beneficial to drinking water treatment. This research applied UV/H₂O₂ for the simultaneous degradation of geosmin, 2-methylisoborneol, four trihalomethanes and six haloacetic acids. Experiments were conducted in de-ionized water at 24 ± 1.0 °C with ng/L amounts of odorants and μg/L amounts of disinfection byproducts. UV was applied with and without 6 mg/L H₂O_2. The results demonstrated that brominated trihalomethanes and brominated haloacetic acids were degraded to a greater extent than geosmin and 2-methylisoborneol. Tribromomethane and dibromochloromethane were degraded by 99% and 80% respectively at the UV dose of 1200 mJ/cm² with 6 mg/L H₂O₂, whereas 90% of the geosmin and 60% of the 2-methylisoborneol were removed. Tribromoacetic acid and dibromoacetic acid were degraded by 99% and 80% respectively under the same conditions. Concentrations of trichloromethane and chlorinated haloacetic acids were not substantially reduced under these conditions and were not effectively removed at doses designed to remove geosmin and 2-methylisoborneol. Brominated compounds were degraded primarily by direct photolysis and cleavage of the C-Br bond with pseudo first order rate constants ranging from 10⁻³ to 10⁻² s⁻¹. Geosmin and 2-methylisoborneol were primarily degraded by reaction with hydroxyl radical with direct photolysis as a minor factor. Perchlorinated disinfection byproducts were degraded by reaction with hydroxyl radicals. These results indicate that the UV/H₂O₂ can be applied to effectively control both odorants and brominated disinfection byproducts.     

Ultrasound-assisted photo-Fenton process for treatment of pulp and paper mill wastewater and reduction of phytotoxicity

The efficiency of classical Fenton (CF) and modified Fenton (MF) as well as photo-Fenton processes in real wastewater treatment of pulp and paper (P&P) mill was investigated in this study. The chemical oxygen demand (COD) was chosen as the reference measurement for evaluating the treatment's efficiency. After determining the optimum parameters for each process, the effect of adding ultrasound (US) on improving treatment efficiency was examined. In addition, kinetic study and phytotoxicity analysis were conducted under optimum conditions for all processes. With pH 4, reaction time 50 min, 1.2 g/L Fe²⁺ and 8 g/L H₂O₂ dosages, the best removal efficiency (RE) of COD was determined to be 82.18% in CF process, and this rate rose to 90.1% when US was added. The best RE in MF process was 84.16% with the application of UV-C, pH 4, reaction time 50 min, 1 g/L Fe⁰ and 8 g/L H₂O₂ doses, although it increased to 93.4% when US was applied. The greatest results in the seed germination test were achieved in US processes with 100% of germination percentage (GP) for spinach and tomato and 90% for cress. In the economic evaluation, when conducting the treatment without US, the estimated relative cost decreased in a 15 and 16%, for CF/UV-C and CF processes respectively, whereas the CF process was 64% cheaper than the MF process in all applications. The US contributed to enhanced water treatment efficiency by having a significant synergistic impact on Fenton applications. Hence, the combination of photo-Fenton and ultrasound to treat effluent from P&P mills proved to be an effective and promising technique.     

The effect of humic acids on nitrobenzene oxidation by ozonation and O3/UV processes

Three types of commercially available humic acids from different sources were used to simulate natural organic matter in water for the investigation of nitrobenzene oxidation by ozonation and O(3)/UV. Despite the structural differences among the Fluka, Aldrich and Suwanee River humic acids as reflected by the UV absorptivity, their effects on nitrobenzene removal rate was observed to be similar for the two processes. Removal rate of nitrobenzene was hindered by the addition of humic acids in ozonation as well as in O(3)/UV processes. However, the hindrance by the humic acids was more pronounced in O(3)/UV as compared to the ozonation process. The effect of humic acid in O(3)/UV was primarily a UV light screening. Addition of humic acids above a certain concentration did not cause any further retardation on nitrobenzene removal rate by ozonation and O(3)/UV.Accumulation of hydrogen peroxide as well as probable formation of peroxy radicals in the solutions might induce chain promoting reactions to produce hydroxyl radical during the nitrobenzene oxidation. For waters containing high levels of humic acid, ozonation alone might be as effective as O(3)/UV process for the removal of nitrobenzene.     

Efficiency and energy requirements for the transformation of organic micropollutants by ozone, O3/H2O2 and UV/H2O2

The energy consumptions of conventional ozonation and the AOPs O₃/H₂O₂ and UV/H₂O₂ for transformation of organic micropollutants, namely atrazine (ATR), sulfamethoxazole (SMX) and N-nitrosodimethylamine (NDMA) were compared. Three lake waters and a wastewater were assessed. With p-chlorobenzoic acid (pCBA) as a hydroxyl radical (^•OH) probe compound, we experimentally determined the rate constants of organic matter of the selected waters for their reaction with ^•OH (k_OH,DOM), which varied from 2.0 × 10⁴ to 3.5 × 10⁴ L mgC⁻¹ s⁻¹. Based on these data we calculated ^•OH scavenging rates of the various water matrices, which were in the range 6.1-20 × 10⁴ s⁻¹. The varying scavenging rates influenced the required oxidant dose for the same degree of micropollutant transformation. In ozonation, for 90% pCBA transformation in the water with the lowest scavenging rate (lake Zürich water) the required O₃ dose was roughly 2.3 mg/L, and in the water with the highest scavenging rate (Dübendorf wastewater) it was 13.2 mg/L, corresponding to an energy consumption of 0.035 and 0.2 kWh/m³, respectively. The use of O₃/H₂O₂ increased the rate of micropollutant transformation and reduced bromate formation by 70%, but the H₂O₂ production increased the energy requirements by 20-25%. UV/H₂O₂ efficiently oxidized all examined micropollutants but energy requirements were substantially higher (For 90% pCBA conversion in lake Zürich water, 0.17-0.75 kWh/m³ were required, depending on the optical path length). Energy requirements between ozonation and UV/H₂O₂ were similar only in the case of NDMA, a compound that reacts slowly with ozone and ^•OH but is transformed efficiently by direct photolysis.     

Impact of UV/H(2)O(2) advanced oxidation treatment on molecular weight distribution of NOM and biostability of water

The presence of natural organic matter (NOM) poses several challenges to the commercial practice of UV/H₂O₂ process for micropollutant removal. During the commercial application of UV/H₂O₂ advanced oxidation treatment, NOM is broken down into smaller species potentially affecting biostability by increasing Assimilable Organic Carbon (AOC) and Biodegradable Organic Carbon (BDOC) of water. This work investigated the potential impact of UV/H₂O₂ treatment on the molecular weight distribution of NOM and biostability of different water sources. A recently developed flow cytometric method for enumeration of bacteria was utilized to assess biological stability of the treated water at various stages through measurement of AOC. BDOC was also assessed for comparison and to better study the biostability of water. Both AOC and BDOC increased by about 3-4 times over the course of treatment, indicating the reduction of biological stability. Initial TOC and the source of NOM were found to be influencing the biostability profile of the treated water. Using high performance size exclusion chromatography, a wide range of organic molecule weights were found responsible for AOC increase; however, low molecular weight organics seemed to contribute more. Positive and meaningful correlations were observed between BDOC and AOC of different waters that underwent different treatments.     

UV/H2O2/微曝气处理微污染水中苯胺的试验研究

采用UV/H2O2/微曝气、UV/H2O2、UV/微曝气、H2O2/微曝气四种工艺处理受苯胺污染的水源水.试验结果表明,采用UV/H2O2/微曝气工艺,H2O2投加量分别为1,2,5,10和20 mL,对苯胺均有理想的去除效果.随着投加量的增加,苯胺的去除率并没有明显的提高,反应30 min后去除率分别达到94.3%,96.4%,96.5%,97.3%和96.8%.原水苯胺为0.90 mg/L时,投加1 mL H2O2反应30 min后,出水苯胺为0.06 mg/L,满足标准要求.UV/H2O2/微曝气、UV/H2O2、UV/微曝气、H2O2/微曝气四种工艺对苯胺的去除率均随着时间的增长而提高,40 min后趋于平稳,最高去除率分别为97.9%,94.5%,64.27%和13.84%,UV/H2O2/微曝气、UV/H2O2出水苯胺均低于规定限值.     

Mechanisms of N2O production in biological wastewater treatment under nitrifying and denitrifying conditions

Nitrous oxide (N₂O) is an important greenhouse gas and a major sink for stratospheric ozone. In biological wastewater treatment, microbial processes such as autotrophic nitrification and heterotrophic denitrification have been identified as major sources; however, the underlying pathways remain unclear. In this study, the mechanisms of N₂O production were investigated in a laboratory batch-scale system with activated sludge for treating municipal wastewater. This relatively complex mixed population system is well representative for full-scale activated sludge treatment under nitrifying and denitrifying conditions.Under aerobic conditions, the addition of nitrite resulted in strongly nitrite-dependent N₂O production, mainly by nitrifier denitrification of ammonia-oxidizing bacteria (AOB). Furthermore, N₂O is produced via hydroxylamine oxidation, as has been shown by the addition of hydroxylamine. In both sets of experiments, N₂O production was highest at the beginning of the experiment, then decreased continuously and ceased when the substrate (nitrite, hydroxylamine) had been completely consumed. In ammonia oxidation experiments, N₂O peaked at the beginning of the experiment when the nitrite concentration was lowest. This indicates that N₂O production via hydroxylamine oxidation is favored at high ammonia and low nitrite concentrations, and in combination with a high metabolic activity of ammonia-oxidizing bacteria (at 2 to 3 mgO₂/l); the contribution of nitrifier denitrification by AOB increased at higher nitrite and lower ammonia concentrations towards the end of the experiment.Under anoxic conditions, nitrate reducing experiments confirmed that N₂O emission is low under optimal growth conditions for heterotrophic denitrifiers (e.g. no oxygen input and no limitation of readily biodegradable organic carbon). However, N₂O and nitric oxide (NO) production rates increased significantly in the presence of nitrite or low dissolved oxygen concentrations.     

Kinetics and mechanisms of DMSO (dimethylsulfoxide) degradation by UV/H(2)O(2) process

The objective of this study was to elucidate the degradation pathways of dimethylsulfoxide (DMSO) during its mineralization caused by UV/H(2)O(2) treatment. In order to accomplish this, we measured the concentration time-profiles of DMSO and its degradation intermediates during the UV/H(2)O(2) treatment. In addition, we proposed a kinetic model that could account for the degradation pathways of DMSO during its UV/H(2)O(2) treatment. The results show that the degradation of DMSO by the UV/H(2)O(2) treatment can be classified into two major pathways, and this is supported by both the analysis of the intermediates and total organic carbon (TOC) measurements. Firstly, DMSO was degraded into sulfate (SO(4)(2-)) through the formation of methansulfinate (CH(3)SO(2)(-)) and methansulfonate (CH(3)SO(3)(-)) as sulfur-containing intermediates. One of the two carbon constituents of DMSO was highly resistant to mineralization, due to the formation of methansulfonate, which reacted very slowly with (.-)OH k = 0.8 x 10(7) M(-1)s(-1)). Secondly, the other carbon constituent of DMSO was relatively easily mineralized through the formation of formaldehyde (HCHO) and formate (HCO(2)(-)) as non-sulfur-containing intermediates. The kinetic model proposed in this study for the degradation of DMSO by (.-)OH in the UV/H(2)O(2) process was able to successfully predict the patterns of concentration time-profiles of all components during the UV/H(2)O(2) treatment of DMSO.