Toxicity and Biodegradability Behavior of Xenobiotic Chemicals Before and After Ozonation: A Case Study with Commercial Textile Tannins

Ozonation of a natural tannin (NT; COD_o?=?1195 mg/L; TOC_o?=?342 mg/L; BOD_5,o?=?86 mg/L) and a synthetic tannin ST; COD_o?=?465 mg/L; TOC_o?=?55 mg/L; BOD_5,o?=?6 mg/L) being frequently applied in the polyamide dyeing process was investigated. Synthetic wastewater samples containing these tannins individually were prepared and subjected to ozonation at varying ozone doses (625– 1250 mgO₃/L wastewater), at pH?=?3.5 (the application pH of tannins) and pH?=?7.0 at an ozone dose of 1125 mgO₃/L wastewater. The collective environmental parameters COD, TOC, BOD₅, UV₂₅₄ and UV₂₈₀ (UV absorbance at 254 nm and 280 nm, representing aromatic and unsaturated moieties, respectively) were followed during ozonation. Changes in the biodegradability of the tannins were evaluated in terms of BOD₅ measurements conducted before and after ozonation. In addition, activated sludge inhibition tests employing heterotrophic biomass were run to elucidate the inhibitory effect of raw and ozonated textile tannins towards activated sludge biomass. Partial oxidation (45% COD removal at an ozone dose of 750 mg O₃/L wastewater and pH?=?3.5) of ST was sufficient to achieve elimination of its inhibitory effect towards heterotrophic biomass and acceptable biodegradability improvement, whereas the inhibitory effect and biodegradability of NT could not be reduced via ozonation under the same reaction conditions.     

Integration of continuous biological and chemical (ozone) treatment of domestic wastewater: 1. Biodegradation and post‐ozonation

The continuous treatment of domestic wastewater by an activated sludge process and by an integrated biological–chemical (ozone) oxidation process were studied in this work. Chemical oxygen demand (COD), biochemical oxygen demand (BOD), absorbance at 254 nm (UV₂₅₄) and nitrogenous compound content were the parameters followed in order to evaluate the performance of the two processes. Experimental data showed that both UV₂₅₄ and COD reductions are improved in the combined biological–chemical oxidation procedure. Thus, reductions of 59.1% and 37.2% corresponding to COD and UV₂₅₄, respectively were observed after the biological process (hydraulic retention time = 5 h; mixed liquor volatile suspended solids concentration = 3142 g m⁻³) compared with 71.0% and 78.4% obtained when a post‐ozonation step ( D _O3 = 41.7 g m⁻³) was included. During conventional activated sludge treatment, appropriate nitrification levels are only achieved with high hydraulic retention time and/or biomass concentration. Ozonation after the secondary treatment, however, allows improved nitrogen content reduction with total nitrite elimination. Post‐ozonation also leads to a higher biodegradability of the treated wastewater. Thus, the ultimate BOD/COD ratio goes from 0.16 after biological oxidation to 0.34 after post‐ozonation with 41.7 g O₃ m⁻³. © 1999 Society of Chemical Industry     

Incidence of an Ozonation Stage on the Treatment of Cherry Stillage by Activated Sludge

This article presents a laboratory study of the ozonation of diluted cherry stillage, a high-strength wastewater. Influence of variables, kinetics, and the effects of an ozonation stage coupled with the biological treatment by activated sludge are addressed. Single activated sludge processing was shown effective to remove biological oxygen demand (BOD) and chemical oxygen demand (COD) but polyphenols were reduced to a lesser extent. On the other hand, direct wastewater ozonation did not reduce COD and total organic carbon (TOC) appreciably, and foaming problems were experienced when a high gas flow rate was applied. However, polyphenols and UV₂₅₄ absorbance decreased substantially by means of ozonation. To best achieve complete cherry stillage purification, two ways of coupling ozonation with activated sludge are proposed. Ozonation prior to activated sludge is advised for high-concentration wastewater to reduce polyphenol concentration, thus removing inhibiting effects. For wastewater with low polyphenol concentration the sequence activated sludge–ozonation–activated sludge is preferred to enhance the overall process performance in terms of oxidation efficiency and sludge settling.     

Advanced oxidation of raw and biotreated textile industry wastewater with O3, H2O2 /UV‐C and their sequential application

The advanced chemical oxidation of raw and biologically pretreated textile wastewater by (1) ozonation, (2) H₂O₂ /UV − C oxidation and (3) sequential application of ozonation followed by H₂O₂ /UV − C oxidation was investigated at the natural pH values (8 and 11) of the textile effluents for 1 h. Analysis of the reduction in the pollution load was followed by total environmental parameters such as TOC, COD, UV–VIS absorption kinetics and the biodegradability factor, f_B. The successive treatment combination, where a preliminary ozonation step was carried out prior to H₂O₂ /UV − C oxidation without changing the total treatment time, enhanced the COD and TOC removal efficiency of the H₂O₂ /UV − C oxidation by a factor of 13 and 4, respectively, for the raw wastewater. In the case of biotreated textile effluent, a preliminary ozonation step increased COD removal of the H₂O₂ /UV − C treatment system from 15% to 62%, and TOC removal from 0% to 34%. However, the sequential process did not appear to be more effective than applying a single ozonation step in terms of TOC abatement rates. Enhancement of the biodegradability factor (f_B) was more pronounced for the biologically pretreated wastewater with an almost two‐fold increase for the optimized Advanced Oxidation Technologies (AOTs). For H₂O₂ /UV − C oxidation of raw textile wastewater, apparent zero order COD removal rate constants (k_app), and the second order OH· formation rates (r_i) have been calculated. © 2001 Society of Chemical Industry     

Post-Treatment of Pulp and Paper Industry Wastewater by Advanced Oxidation Processes

The aim of this study was to investigate the effectiveness of chemical oxidation by applying ozonation, combination of ozone and hydrogen peroxide and Fenton's processes for decolorization and residual chemical oxygen demand (COD) removal of biologically pretreated pulp and paper industry effluents. The batch tests were performed to determine the optimum operating conditions including pH, O₃, H₂O_2, and Fe²⁺ dosages. H₂O₂ addition reduced the reaction times for the same ozone dosages; however combinations of ozone/hydrogen peroxide were only faintly more effective than ozone alone for COD and color removals. In the Fenton‘s oxidation studies, the removal efficiencies of COD, color and ultraviolet absorbance at 254 nm (UV₂₅₄) for biologically treated pulp and paper industry effluents were found to be about 83, 95, and 89%, respectively. Experimental studies indicated that Fenton oxidation was a more effective process for the reduction of COD, color, and UV₂₅₄when compared to ozonation and ozone/hydrogen peroxide combination. Fenton oxidation was found to have less operating cost for color removal from wastewater per cubic meter than the cost for ozone and ozone/hydrogen peroxide applications.     

The degradation of an azo dye in a batch slurry photocatalytic reactor

The photocatalytic degradation of a commercial azo-reactive textile dye, Remazol Red F-3B, has been investigated in a batch slurry reactor using semiconductor catalysts like, ZnO and TiO₂, and two UV sources emitting mainly at 254 and 365 nm. Non-irradiated catalysts and non-catalyzed UV irradiation have negligible effect on the dye degradation. Initial pH, dye concentration, light power and catalyst loading as well as the catalyst type and UV wavelength are considered as process variables. The results showed that decolorization and TOC removal efficiencies of ZnO are higher under 365 nm UV. On the other hand, when two photocatalysts are compared, the decolorization performance of ZnO is higher than TiO₂ under 365 nm UV_, while TiO₂ performs better under 254 nm UV. Furthermore, from the TOC removal point, TiO₂ performs better than ZnO irrespective of the UV wavelength. TiO₂ irradiated under 254 nm UV degrades successfully both benzene and naphthalene derivatives.     

Toxicity Assay in Kraft E1 Effluent Treated by Ozone: Algae Growth Inhibition and Cytotoxicity in V79 Cells

The efficiency of an ozonation process in the degradation of the Kraft E₁ effluent was evaluated. The investigation was focused on the reduction of chemical oxygen demand, total phenols, color and the absorbance at 254 nm. The chronic toxicity was evaluated by growth inhibition of algae Selenatrum capricornutum and cytotoxicity evaluation of effluents samples by determination of the nucleic acid content (NCA) endpoint. After 60 minutes of ozonation, COD and UV₂₅₄ only reached 21% and 34% efficiency reduction. Total phenols and color were more rapidly removed (at 10 minutes of treatment). The results showed that the chronic toxicity (Selenastrum capricornutum algae) decreases for all effluent doses studied. The cytotoxicity assay indicated that toxic compounds were not generated by the ozonation process.     

Ozonation of humic acid in water

BACKGROUND: Humic acids (HAs) are heterogeneous macromolecules widely dispersed in natural waters, which display significant resistance to biodegradation. Removal of HA by ozone and its related reaction mechanisms are investigated. RESULTS: Ozonation of HA showed a significant reduction of UV₂₅₄, Color₄₃₆ and had the capability of mineralizing the TOC to CO₂ and improving the biodegradability. Fourier trandform infrared (FT‐IR) spectra, elemental composition analysis and high performance size exclusion chromatography (HPSEC) revealed that ozonation could not only change the structure characteristics but modify the molecular size distribution of HA. Volatile compounds detected by gas chromatography‐mass spectroscopy (GC‐MS) showed that ozonation brought out 43 different organics, which were identified as mainly: aldehydes, ketones, aromatics, carboxylic acids and alcohols. CONCLUSION: Ozonation of HA could be elucidated by the followed mechanism: ozonation with its direct and indirect pathway hydroxylated the HA in water, and polyhydroxy HA was further oxidized to bond rupture leading to the change of molecular structure and size distribution of HA, trimming out a series of small molecular volatile compounds. The volatile compounds with electron denoting group could be further oxidized to acids and esters, and even totally mineralized to CO₂. Copyright © 2007 Society of Chemical Industry     

Degradation and Transformation of Organic Compounds in Songhua River Water by Catalytic Ozonation in the Presence of TiO2/Zeolite

This paper presents experimental results of the catalytic ozonation of Songhua River water in the presence of nano-TiO₂ supported on Zeolite. The removal efficiency of TOC and UV₂₅₄, the variation of AOC and molecular weight distribution of organics was studied. Results showed that TOC and UV₂₅₄ removal efficiency by ozone was improved in the presence of TiO₂/Zeolite, and increased by 20% and 25%, respectively. The part of organic compounds less than 1000 Da increased in ozonation, but decreased in catalytic ozonation. The AOC of water increased in catalytic ozonation, and the increase of AOC was particularly obvious when ozone dose increased from 28.8 mg·L^?1 to 46.6 mg·L^?1. The degradation and transformation of organic compounds was analyzed by means of GC-MS. The total number of organic compounds was reduced from 50 in the untreated water to 36 and 20, respectively, in ozonation and catalytic ozonation. The removal efficiency of the total organic compounds peak area in ozonation and catalytic ozonation were 23.5% and 62.5%, respectively. Most of the hydrocarbons could be removed easily in ozonation and catalytic ozonation. The organic compounds having hydroxyl, carboxyl or carbonyl groups were hard to be removed in ozonation, but could be removed efficiently in the presence of TiO₂/Zeolite.     

Removal of Residual Dissolved Ozone with Manganese Dioxide for Process Control with UV254

Ozonation is one of the most promising options to remove organic micropollutants (OMP) from wastewater treatment plant effluents. For an economic operation and in order to avoid formation of bromate, the ozone dose has to be adjusted in real-time due to the strongly varying effluent quality. The reduction of UV absorption at 254 nm (?UV₂₅₄) is a useful surrogate parameter for OMP removals. Unfortunately dissolved ozone also absorbs UV at 254 nm and therefore might disturb a ?UV₂₅₄-based process control. A fixed bed of manganese dioxide granules was found to efficiently remove residual ozone.     

Effect of temperature on the ozonation of textile waste effluent

Ozonation in batch experiments were conducted at elevated temperatures to study the influence of temperature on the efficiency of ozonation. The effect of temperature on ozonation was determined by measuring the extent of colour removal and the reduction of chemical oxygen demand (COD) and total organic carbon (TOC) of a textile waste effluent. It was found that increasing the temperature causes a decrease in the levels of colour, COD and TOC. Complete mineralisation of the dye molecule, however, did not occur to an appreciable extent. The efficiency of colour removal was 71.3%, whilst the COD and TOC reduction efficiency was 20.3 and 19.3%, respectively, at the highest temperature studied (50 °C). The removal efficiency of COD, however, did not improve significantly when the temperature was increased from 40 to 50 °C.     

Pilot Study on Pre-Ozonation Enhanced Drinking Water Treatment Process

The enhancement of TOC, COD_Mn, and UV₂₅₄ reduction in the conventional drinking water treatment process by pre-ozonation was investigated in South China on treating dam source water with a pilot plant consisting of pre-ozonation, coagulation-sedimentation, and filtration units. Pre-ozonation enhanced the reduction of NOM in the conventional coagulation-sedimentation and filtration process, and the total removals of UV₂₅₄, COD_Mn and TOC were improved for 34.6%, 18.1% and 15.3%, respectively by the adoption of pre-ozonation under an ozone dose (in ozone consumption base) of 0.85 mg/L. The enhancement of UV₂₅₄ and COD_Mn removals was mainly achieved through direct ozonation on humic substances, and that for TOC removal was achieved through biodegradation in sand filtration. In comparison with the TOC removal of 38%, a removal of 49% was acquired for SDS-THM under a pre-ozonation dose of 0.80 mg/L, indicating the selective removal of THMFP. The reduction of SDS-THM paralleled the reduction of COD_Mn to a significant degree, suggesting that the COD_Mn might be an effective surrogate parameter for SDS-THM if the raw water does not contain the reductive inorganic matters. Although the source water contains 13.2–27.0μg/L bromide, the formation of bromate was negligible when the ozone dose was below 1.0 mg/L.     

The Effect Of Preozonation,Ozone/Hydrogen Peroxide Treatment,And Nanofiltration On The Removal Of Organic Matter From Drinking Water

Pilot scale experiments were performed to evaluate the ability of ozonation, ozone/hydrogen peroxide treatment and nanofiltration to reduce levels of organic matter, mutagenicity, total adsorbable halogens, color and turbidity from purified and bank-filtered surface water rich with humic material.

Ozonation and ozone/hydrogen peroxide decreased the amount of organic material from drinking water by about 20 percent measured as TOC and COD_Mn. Color and turbidity level reductions were 49 and 11 percent, respectively. Ozonation reduced the AOX concentrations formed during postchlorination from 150 μgL^?1 to 75 μgL^?1. The addition of hydrogen peroxide further improved the removal to 37 and 26 μgL^?1 depending on the ratio of H₂O₂/O₃. The mutagenicity reduction followed the same pattern: without ozonation the chlorination-derived mutagenicity was 1,450 net revertant L^?1 after the ozonation 700 and after the H₂O₂/O₃ treatment from <100 to 400 net revertant L^?1 depending on the H₂O₂/O₃ ratio. Nanofiltration appeared to be the most effective way to remove organic material. The removal of TOC was 68%, COD_M 72%, color 90%, turbidity 68%, AOX 88%, and mutagenicity 85%.     

Modelling Industrial Wastewater Ozonation In Bubble Contactors. 1. Rate Coefficient Determination

A study of the ozonation of distillery and tomato wastewaters was carried out in a small bubble contactor in order to obtain kinetic data for scaling-up. Thus, several parameters, such as chemical oxygen demand (COD), 254 nm absorbance (A₂₅₄) and organic carbon content (OC), were followed during ozonation at different experimental conditions.

For distillery wastewaters all parameters investigated have the highest decreases during the first minutes of ozonation, A₂₅₄ showing the highest disappearance rates. Thus, during the first fifteen minutes of ozonation an important decrease of the 254 nm absorbance (? 75%) was observed. At further reaction times values of all parameters studied decrease slowly, eventually reaching a plateau value. During approximately the first two hours of reaction, dissolved ozone was never found, which suggested that fast or moderate gas-liquid reactions took place in the wastewaters.     

Ozone/H2O2 Performance on the Degradation of Sulfamethoxazole

This work aims to analyze the contribution of H₂O₂ on ozonation of Sulfamethoxazole (SMX). A single ozonation was able to totally remove SMX. TOC and COD depletion rates after a transferred ozone dose of 60 mg/L was related to the formation and decomposition of H₂O₂. An increase on O₃ gas inlet concentration from 10 g/m³ to 20 g/m³ improved COD abatement from 11% to 36%. When the presence of H₂O₂ at the beginning of ozonation was tested, it was verified that COD and TOC degradation were enhanced, attaining maximum values of 76% and 32%, respectively, when compared with 35% and 15% reached in a single ozonation.     

Removal Characteristics of Organic Pollutants in Sewage Treatment by a Pre-Coagulation,Ozonation and Ozone/Hydrogen Peroxide Process

The applicability of a sequential process of ozonation and ozone/hydrogen peroxide process for the removal of soluble organic compounds from a pre-coagulated municipal sewage was examined. 6–25% of initial T-COD_Cr was removed at the early stage of ozonation before the ratio of consumed ozone to removed T-COD_Cr dramatically increased. Until dissolved ozone was detected, 0.3 mgO₃/mgTOC₀ (Initial TOC) of ozone was consumed. When an ozone/hydrogen peroxide process was applied, additional COD_Cr was removed. And we elucidated that two following findings are important for the better performance of ozone/hydrogen peroxide process; those are to remove readily reactive organic compounds with ozone before the application of ozone/hydrogen peroxide process and to avoid the excess addition of hydrogen peroxide. Based on these two findings, we proposed a sequential process of ozonation and multi-stage ozone/hydrogen peroxide process and the appropriate addition of hydrogen peroxide. T-COD_Cr, TOC and ATU-BOD₅ were reduced to less than 7 mg/L, 6 mgC/L and 5 mg/L, respectively after total treatment time of 79 min. Furthermore, we discussed the transformation of organic compounds and the removal of organic compounds. The removal amount of COD_Cr and UV₂₅₄ had good linear relationship until the removal amounts of COD_Cr and UV₂₅₄ were 30 mg/L and 0.11 cm^?1, respectively. Therefore UV₂₅₄ would be useful for an indicator for COD_Cr removal at the beginning of the treatment. The accumulation of carboxylic acids (formic acid, acetic acid and oxalic acid) was observed. The ratio of carbon concentration of carboxylic acids to TOC remaining was getting higher and reached around 0.5 finally. Removal of TOC was observed with the accumulation of carboxylic acids. When unknown organic compounds (organic compounds except for carboxylic acids) were oxidized, 70% was apparently removed as carbon dioxide and 30% was accumulated as carboxylic acids. A portion of biodegradable organic compounds to whole organic compounds was enhanced as shown by the increase ratio of BOD/COD_Cr.     

Impact of Ozonation on Decolorization and Mineralization of Azo Dyes: Biodegradability Enhancement,By-Products Formation,Required Energy and Cost

In the present study ozonation process was implemented to analyze the effect of ozonation time on the rate of chemical oxygen demand (COD) removal, mineralization and rate of decolorization of azo dyes. Three types of azo dyes i.e. Acid Red 14, Direct Red 28 and Reactive Black 5 were selected. Decolorization and mineralization of samples were conducted in batch scale. The COD and color removal efficiency were found to be increasing at a certain time of ozonation. The results with Acid Red 14, Congo Red and Reactive Black 5 dyes solutions lead to maximum COD reduction of 75%, 67% & 50% respectively. 93%, 92% and 94% color removal were achieved after 25 min of ozonation time of the same dyes which highlighted that ozonation process was found to be more efficient for reactive dye decolorization. Ozonation by-products analyzed by ion chromatography resulted that it partially mineralized with the formation of chloride, fluoride, sulphate, nitrate and oxalate ions. During ozonation process a rapid decrease in pH value indicated the acidic nature of by-products. The effect of buffered dye solutions on the ozonoation process highlighted that the decolorization efficiency decreases in comparison to unbuffered dye solutions. Ozonation led to enhancement of biodegradability ratio (BOD₅/COD) and increased electrical conductivity of the dye solutions. Optimum ozonation time required for degradation of dye solutions reflected the evaluation of energy consumption and cost of the treatment after ozonation.     

Removal of organic contaminants in paper pulp effluents by AOPs: an economic study

The degradation of the organic content of a bleaching Kraft mill effluent was carried out using Advanced Oxidation Processes (AOPs). The study was focused on the identification of the AOP, or combination of AOPs, that showed the highest efficiency together with the lowest cost. Direct UV photolysis (UV), TiO₂ assisted‐photocatalysis (TiO₂/UV), Fenton, Fenton‐like, and photo‐Fenton reactions (Fe(II)/H₂O/UV), UV‐assisted ozonation (O₃/UV) and addition of Fe²⁺ and/or H₂O₂ to the TiO₂/UV and the O₃/UV systems, were used for the degradation of a conventional cellulose bleaching effluent. The effluent was characterized by the general parameters TOC, COD and color, and analyzed for chlorinated low molecular weight compounds using GC–MS. The costs of the systems per unit of TOC reduction were compared. Fenton, Fenton‐like and photo‐Fenton reactions achieved better levels of TOC degradation than photocatalysis and with lower cost's than photocatalytic treatments. Ozonation is an effective but rather expensive process. The use of UVA light, however, increased the effectiveness of ozonation with a significant decrease (>25%) in the operational cost. © 2002 Society of Chemical Industry     

Photoelectrocatalytic humic acid degradation kinetics and effect of pH,applied potential and inorganic ions

This study addresses the removal of humic acid (HA) dissolved in an aqueous medium by a photoelectrocatalytic process. UV₂₅₄ removal and the degradation of color (Vis₄₀₀) followed pseudo‐first order kinetics. Rate constants were 1.1 × 10^?1 min^?1, 8.3 × 10^?2 min^?1 and 2.49 × 10^?2 min^?1 (R² > 0.97) for UV₂₅₄ degradation and 1.7 × 10^?1 min^?1, 6.5 × 10^?2 min^?1 and 2.0 × 10^?2 min^?1 for color removal from 5 mg dm^?3, 10 mg dm^?3 and 25 mg dm^?3 HA respectively. Following a 2 h irradiation time, 96% of the color, 98% of the humic acid and 85% of the total organic carbon (TOC) was removed from an initial 25 mg dm^?3 HA solution in the photoanode cell. Photocatalytic removal on the same photoanode was also studied in order to compare the two methods of degradation. Results showed that the photoelectrocatalytic method was much more effective than the photocatalytic method especially at high pH values and with respect to UV₂₅₄ removal. The effect of other important reaction variables, eg pH, external potential and electrolyte concentration, on the photoelectrocatalytic HA degradation was also studied. Copyright © 2003 Society of Chemical Industry     

Effect of ozonation on chemical oxygen demand fractionation and color profile of textile wastewaters

Filtration and ultrafiltration with a size range of 2–1600 nm were used to evaluate the effect of ozonation on the particle size distribution‐based chemical oxygen demand (COD) and color profiles of textile wastewater before and after biological treatment. Ozonation induced a net effect of 9% COD reduction in the influent and 15% in the effluent. However, a more in‐depth evaluation based on particle size distribution and mass balance for the influent revealed different mechanisms of ozonation, which were interpreted as total oxidation in the soluble range, replenishment of soluble COD through solubilization of organics into simpler compounds and polymerization towards the upper size range (>220 nm). For the biological treatment effluent, the greatest effect of ozonation was in the lower particle size range (<8 nm). Ozone was very effective for color removal, giving 80–93% optical density reductions in the influent and 96–99% in the effluent, depending on the excitation wavelength selected. Ozonation of the influent removed practically all color fractions, except in the particulate range. In the effluent, the particulate fraction was removed by biological treatment and settling and consequently the remaining color were almost entirely removed by ozonation. Copyright © 2005 Society of Chemical Industry